Document [original]

Hydrogen Bonding in Platinum Indolylphosphine

Polyfluorido and Fluorido Complexes

Stefan Sander,[a] Elizabeth J. Cosgrove,[a] Robert Müller,[b] Martin Kaupp,*[b] and

Thomas Braun*[a]

Abstract: The reaction of the Pt complexes cis-[Pt(CH3)(Ar)-

{Ph2P(Ind)}2] (Ind=2-(3-methyl)indolyl, Ar=4-tBuC6H4(1a),4-

CH3C6H4(1b), Ph (1c), 4-FC6H4(1d), 4-ClC6H4(1e), 4-CF3C6H4

(1f)) with HF afforded the polyfluorido complexes trans-

[Pt(F(HF)2)(Ar){Ph2P(Ind)}2]2a–f, which can be converted into

the fluoride derivatives trans-[Pt(F)(Ar){Ph2P(Ind)}2] (3a–f) by

treatment with CsF. The compounds 2a–fand 3a–fwere

characterised thoroughly by multinuclear NMR spectroscopy.

The data reveal hydrogen bonding of the fluorido ligand with

HF molecules and the indolylphosphine ligand. Polyfluorido

complexes 2a–fshow larger j1J(F,Pt)j, but lower 1J(H,F)

coupling constants when compared to the fluorido com-

plexes 3a–f. Decreasing 1J(P,Pt) coupling constants in 2a–f

and 3a–fsuggest a cis influence of the aryl ligands in the

following order: 4-tBuC6H4(a)�4-CH3C6H4(b)<Ph (c)!4-

FC6H4(d)<4-ClC6H4(e)<4-CF3C6H4(f). In addition, the larger

cis influence of aryl ligands bearing electron-withdrawing

groups in the para position correlates with decreasing

magnitudes of j1J(F,Pt)jcoupling constants. The interpreta-

tion of the experimental data was supported by quantum-

chemical DFT calculations.

Introduction

In the last two decades fluorido complexes of late transition

metals attracted an increasing interest,[1] in part due to their

ability to establish novel routes for metal-mediated

fluorination,[1h,i,l,r,2] but they can also play a distinct role in CF

and CH bond activation reactions.[1j,n,3] Initial studies on the

synthesis of Pt(ii) fluorido complexes were reported in the early

1970’s.[1a,4] They then came back into focus at the begin of the

millennium.[1d,e,5] Strategies reported for the formation of

platinum fluorido complexes include Cl/F exchange reactions

with AgF,[1d,e,5l] fluorination with XeF2[5d,i] as well as with NFSI or

Selectfluor,[5m,n] CF,[5b,c, f] PF[5k] or SF[1p,6] bond activation

reactions, and conversions involving hydrogen fluoride.[4a,5a,g,7]

The potential of transition metal fluorido complexes to act as

hydrogen bond acceptors[1k,8] is of certain interest to control

reactivity, for example by modulating the effective nucleophilic-

ity of the fluoride through lowering its basicity,[9] or by

stabilisation of the fluoride in the outer ligand-sphere.[7,10] A

familiar route for the generation of bifluorido and polyfluorido

complexes showing intermolecular hydrogen bonding to the

fluorido ligand consists of the utilisation of hydrogen fluoride as

potential hydrogen bond donor molecule.[1m,5a,11] Furthermore,

several examples of complexes were described, where func-

tional ligands - bearing NH or OH groups - form intramolecular

hydrogen bonds to fluorido ligands in the outer ligand-sphere.

Recently, we reported on Pt(ii) (poly-)fluorido complexes

featuring 2-(3-methyl)indolyl substituted phosphines as cooper-

ating ligands, which stabilise (poly)fluorides by intramolecular

hydrogen bonding in the outer ligand sphere.[7] The hydrogen

bonds of NH groups to the fluorido ligand provided unprece-

dented reactivities.[12]

Most notably, the strength of a metal-ligand bond is

affected by the trans influence of the trans coordinated ligand.

For platinum complexes there is a well described correlation

between PtP bond lengths and 1J(P,Pt) coupling constants[13]

that enabled the early estimation of a ligand’s trans-

influence.[13b,14] However, recent studies of complexes of the

type trans-[Pt(X)(Y)(PPh3)2] also emphasised the presence of a

non-negligible cis-influence, i.e. a weakening of the PtP bonds

in the cis positions.[15]

Herein, we report on the formation of the platinum fluorido

complexes trans-[Pt(F)(Ar){Ph2P(Ind)}2] (3a-f) (Ar=4-tBuC6H4

(3a),4-CH3C6H4(3b), Ph (3c), 4-FC6H4(3d), 4-ClC6H4(3e), 4-

CF3C6H4(3f), Ind=2-(3-methyl)indolyl) bearing indolylphos-

phine ligands as well as aryl ligands, which differ by their

substitution pattern at the para position. The complexes were

studied thoroughly by multinuclear NMR and IR-spectroscopy

[a] S. Sander, E. J. Cosgrove, Prof. Dr. T. Braun

Department of Chemistry

Humboldt-Universität zu Berlin

Brook-Taylor-Str. 2, 12489 Berlin (Germany)

E-mail: [email protected]

Homepage: https://www2.hu-berlin.de/chemie/braun

[b] Dr. R. Müller, Prof. Dr. M. Kaupp

Institut für Chemie

Technische Universität Berlin, Theoretische Chemie/Quantenchemie, Sekr.C7

Straße des 17. Juni 135, 10623 Berlin (Germany)

E-mail: [email protected]

Homepage: https://www.quantenchemie.tu-berlin.de

Supporting information for this article is available on the WWW under

https://doi.org/10.1002/chem.202202768

GmbH. This is an open access article under the terms of the Creative

Commons Attribution Non-Commercial NoDerivs License, which permits use

and distribution in any medium, provided the original work is properly cited,

the use is non-commercial and no modifications or adaptations are made.

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Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 106/116] 1

as well as by single crystal X-ray diffraction. NMR data revealed

a notable influence of the various aryl ligands on the 1J(P,Pt)

coupling constants, which show a correlation with the j1J(F,Pt)j

coupling constants as well as with the chemical shifts for the

indolyl NHproton and the fluorido ligand in the 1H, 19F

and1H/15N HMBC NMR spectra.

Results and Discussion

The Pt(ii) methyl aryl complexes cis-[Pt(CH3)(Ar){Ph2P(Ind)}2]

(Ar=4-tBuC6H4(1a),4-CH3C6H4(1b), Ph (1c), 4-FC6H4(1d), 4-

ClC6H4(1e), 4-CF3C6H4(1f)) were synthesised by reactions of

[Pt(Ar)(CH3)(COD)] (Ar=4-tBuC6H4, 4-CH3C6H4,[16] Ph,[17] 4-FC6H4,[18]

4-ClC6H4, 4-CF3C6H4) with two equivalents of diphenyl-2-(3-

methyl)indolylphosphine (Ph2P(Ind)) (Scheme 1). The 1,5-cyclo-

octadiene platinum (ii) precursor complexes were formed by

treating [Pt(Cl)(CH3)(COD)][19] (COD=1,5-cyclooctadiene) with

the appropriate aryl Grignard reagents in THF at 0°C. Com-

plexes 1a-f were characterised by 1H NMR, 31P{1H} NMR as well

as IR spectroscopy, and selected NMR and IR data are listed in

Table 1.

The ATR IR spectra of 1a-f each exhibit two medium-

intensity absorption bands between 3444–3449 cm1and

3361–3370 cm1, respectively, which can be assigned to the

NH stretch of the indolyl groups. Each complex exhibits one

broadened and red shifted absorption band, compared to the

absorption band of the free phosphine ligand precursor

(3445 cm1), which indicates hydrogen bonding in the solid

state.[20] The 1H NMR spectra of 1a–fdisplay two signals for the

NHprotons of the indolyl moiety between 9.03–8.88 and 8.44–

8.52 ppm. Both, the IR and 1H NMR data for the indolyl NH-

group resemble data reported for similar Pt(ii) dimethyl

indolylphosphine complexes.[12] For the platinum bound methyl

ligand a multiplet with 195Pt satellites was observed at δ=0.49–

0.52 ppm with 2J(H,Pt) coupling constants of 67–68 Hz, which

are typical values for platinum methyl complexes.[21] The 31P{1H}

NMR spectra of 1a,1b and 1d–fexhibit two doublets with 195Pt

satellites revealing 2J(P,P) coupling constants <15 Hz, which are

characteristic for phosphorus nuclei in a mutually cis position.[22]

For complex 1c, two overlapping signals with 195Pt satellites

were detected at δ=9.1 ppm. However the 195Pt satellites

clearly showed 2J(P,P) coupling constants of 9.9 Hz. For all

complexes, 1J(P,Pt) coupling constants between 1594–1669 Hz

and 1867–1899 Hz were observed, which are typical values for a

phosphorus nuclei in the trans position to an aryl or a methyl

ligand, respectively.[21,23] Note, that for the PtP bond trans to

the aryl ligand complexes, 1a–cexhibit lower 1J(P,Pt) coupling

constants than 1d–f, which is consistent with a larger trans

influence of the more electron rich tBuC6H4, CH3C6H4and Ph

ligands compared to the 4-FC6H4, 4-ClC6H4and 4-CF3C6H4

ligands featuring electron withdrawing para substituents.[13b,14a, b,

23d, 24]

Furthermore, the molecular structures of cis-[Pt(CH3)(4-

FC6H4){Ph2P(Ind)}2] (1d) and cis-[Pt(CH3)(4-ClC6H4){Ph2P(Ind)}2]

(1e) were determined by single-crystal X-ray diffraction analysis.

Colourless crystals of 1d and 1e were obtained by slow

evaporation of a concentrated solution in CH2Cl2at room

temperature. Selected bond lengths and angles are listed in the

captions of Figure 1. For 1d the asymmetric unit contains two

independent molecules, which show only minor differences of

the bond lengths and angles. Therefore, only the structure of

one molecule will be discussed.

Scheme 1. Syntheses of platinum methyl aryl complexes 1a–f.

Table 1. Selected NMR and IR data of complexes 1a–f.

1H NMR[a] 31P{1H} NMR[a] IR data

Complex δ(NH)

[ppm]

δ(Pt-CH3)

[ppm]

2J(H,Pt)

[Hz]

[ppm]

1J(P,Pt)

[Hz]

v(NH)

[cm1]

1a 9.02

8.52

0.49 68 9.3

9.1

1594

1898

3445 3365

1b 8.88

8.44

0.50 68 9.4

8.6

1615

1888

3449 3370

1c 8.99

8.51

0.51 68 9.1

9.1

1607

1891

3444 3363

1d 8.93

8.50

0.51 67 9.1

9.0

1664

1867

3448 3366

1e 8.90

8.47

0.49 67 9.0

8.8

1670

1870

3444 3368

1f 8.99

8.46

0.51 67 9.1

8.8

1669

1876

3444 3361

[a] all spectra were recorded using CD2Cl2as solvent.

Figure 1. Molecular structure of cis-[Pt(CH3)(4-FC6H4){Ph2P(Ind)}2] (1d) (left)

and cis-[Pt(CH3)(4-ClC6H4){Ph2P(Ind)}2] (1e) (right). Thermal ellipsoids are

drawn at 50% probability level, the intermolecular hydrogen bond is

depicted as a magenta dashed line. The second molecular structure of 1 d,

the solvent molecule and carbon bound hydrogen atoms were omitted for

clarity. Selected bond lengths, distances [Å] and bond angles [°] of 1d: Pt1-

P1 2.3022(7), Pt1-P2 2.3255(7), Pt1-C43 2.113(3), Pt1-C44 2.055(3), P1-Pt1-P2

96.09(2), C43-Pt1-C44 84.90(11), P1-Pt1-C44 91.85(7), P2-Pt1-C43 87.44(8).

Selected bond lengths, distances [Å] and bond angles [°] of 1e: Pt1-P1

2.3105(8), Pt1-P2 2.3208(8), Pt1-C43 2.109(3), Pt1-C44 2.044(3), P1-Pt1-P2

102.82(3), C43-Pt1-C44 82.65(12), P1-Pt1-C44 88.78(8), P2-Pt1-C43 85.55(9).

Chemistry—A European Journal

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Both complexes, 1d and 1e, possess a slightly distorted

square-planar coordination geometry of the two phosphines,

the aryl and methyl ligands bound to Pt. They exhibit P1

Pt1P2 bond angles of 96.09(2) and 102.82(3), while the C43

Pt1C44 bond angle between the methyl and aryl ligand are

smaller with values of 84.90(11) and 82.65(12), respectively. For

each complex the Pt1P1 bond length in a trans position to

the methyl ligand is slightly shorter (2.3022(7) for 1d, 2.3105(8)

for 1e) compared to the Pt1P2 bond length that is located

trans to the aryl ligand (2.3255(7) (1d), 2.3208(8) (1e)). The

Pt1P1, Pt1P2 and the platinum methyl Pt1C43 bond

lengths (2.113(3) (1d), 2.109(3) (1 e)) as well as the platinum aryl

Pt1C44 bond length (2.055(3) (1 d), 2.044(3) (1e)) are in good

accordance with the literature.[21b,23b,25] Additionally, both struc-

tures exhibit intramolecular hydrogen bonding from one NH

group of an 2-(3-methyl)indolyl moiety to the nitrogen atom of

the second indolyl unit.

Recently, it has been reported that protonolysis of platinum

dimethyl complexes bearing indolyl substituted phosphine

ligands with HF sources led to the formation of the Pt(ii) methyl

(poly-)fluorido complexes trans-[Pt(F·(HF)2)(CH3){R2P(Ind)}2]. The

fluorido derivatives trans-[Pt(F)(CH3){R2P(Ind)}2] were generated

by subsequently removing the pendant HF with CsF as a base

(R=Ph, 4-FC6H4, 4-CF3C6H4).[12]

Intrigued by these results we investigated whether proto-

nolysis of the methyl ligand is also feasible for the Pt(ii) methyl

aryl complexes 1a–f. Indeed, when solutions of 1a–fin

dichloromethane were treated with an excess HF on using

poly[4-vinylpyridinium poly(hydrogen fluoride)] (PVPHF; 38–

42 wt% HF) as HF source, an immediate gas evolution was

observed. NMR spectroscopic investigations revealed the for-

mation of the platinum (poly)fluorido complexes trans-[Pt-

(F·(HF)2)(Ar){Ph2P(Ind)}2]2a–fas the main products. However,

cleavage of the PtAr bond was also observed and therefore

trans-[Pt(F(HF)2)(CH3){Ph2P(Ind)}2][12] was detected as minor prod-

uct. Although the amount of the latter varied, the largest

amount of the Pt fluorido methyl complexes was determined to

be 20% (based on signal integration from the 31P{1H} NMR

spectrum) (Scheme 2). The amount of pendant HF at 2a–fwas

determined by treatment of the reaction solutions with Et3SiCl

to yield Et3SiF, the amount of which was determined by

integration in the 19F NMR spectra. When the reaction solutions

of the polyfluorido complexes were stirred over anhydrous CsF

for five minutes, the fluorido complexes trans-[Pt(F)(Ar){Ph2P-

(Ind)}2]3a–f(major) as well as trans-[Pt(F)(CH3){Ph2P(Ind)}2]

(minor) were obtained (Scheme 2).

The fluorido complexes 3a–fwere characterised thoroughly

by 1H, 19F, 31P{1H} NMR as well as 1H/15N HMBC NMR

spectroscopy. For the polyfluorido complexes 2a–fbroad

signals were observed at room temperature and therefore 1H,

19F and 31P{1H} NMR were measured at 30°C. Selected NMR

data are listed in Table 2.

The 1H NMR spectra of 3 a–feach exhibit a downfield shifted

doublet signal at δ=12.93–12.76 ppm, which can be assigned

to the NHproton of the indolyl moieties. The NHgroups

undergo hydrogen bonding to the fluorido ligand, which is in

accordance with the downfield shift, but is also revealed by the

1J(H,F) coupling constants of 48–50 Hz.[7,12] The signals collapse

into singlets in the corresponding 1H{19F} NMR spectra. Addi-

tional data for 3a–fwere obtained from 1H/15N HMBC NMR

spectra. The 2J(N,F) coupling constants decrease slightly from

34 Hz for 3 a to 31 Hz for 3f. The values are characteristic for a

15N-19F spin-spin coupling across a NH···F hydrogen bond,[26]

while the 15N chemical shifts as well as the 1J(N,H) coupling

constants are typical for indoles.[27]

Scheme 2. Formation of platinum (poly)fluorido complexes 2a–fand 3 a–f.

Table 2. Selected NMR data for the fluorido complexes 3 a–f[a] and polyfluorido complexes 2 a–f.[a,b]

1H NMR[a] 19F NMR[a] 1H/15N HMBC NMR[c] 31P{1H} NMR[a]

complex δ(NH) [ppm] 1J(H,F) [Hz] δ(Pt-F) [ppm] j1J(F,Pt)j[Hz] δ(NH) [ppm] 1J(N,H) [Hz] 2J(N,F) [Hz] δ[ppm] 1J(P,Pt) [Hz] 2J(P,F) [Hz]

12.93 11.79 50

38 273.6

267.7

567

639 238

–

5.8

7.1

3176

3164

13.1

13.4

12.91 11.84 50

40 274.0

269.8

564

626 238

–

5.1

6.2

3172

3156

13.0

13.8

12.88 11.87 50

40 275.2

270.0

559

620 238

–

5.5

6.7

3162

3149

13.7

14.2

12.80 12.01 49

41 278.3

274.3

521

583 239

–

5.1

6.0

3112

3099

13.6

13.3

12.76 12.05 49

42 278.7

275.1

519

570 239

–

4.9

5.6

3103

3091

13.7

13.4

12.71 11.92 48

40 280.0

275.9

515

569 239

–

5.5

6.3

3090

3080

13.5

13.7

[a] all spectra were recorded using CD2Cl2as solvent. [b] all spectra were recorded at 243 K.

Chemistry—A European Journal

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The 19F NMR spectra of 3a-f revealed a triplet of triplets

with 195Pt satellites for the fluorido ligands due to coupling with

the NHprotons and the two phosphorus nuclei (Figure 2, top).

The observed chemical shifts between δ=-267.7 ppm –

-280.0 ppm and the 2J(F,P) coupling constants of 13–14 Hz are

typical values for Pt fluorido complexes bearing phosphine

ligands in a cis position.[1e,p,4c,5a,c,f,h,j,k, 6–7,28] The observed j1J(F,Pt)j

coupling constants (567-517 Hz) have comparable values to

those reported for the fluorido complexes trans[-Pt(F)(CH3){R2P-

(Ind)}2] (R=Ph, 4-FC6H4, 4-CF3C6H4).[12]

For the polyfluorido complexes 2a–fthe 1J(H,F) coupling

constants to the indolyl moiety show smaller values (38–42 Hz)

and the chemical shifts of the NHprotons appear at higher field

between δ=11.79-12.05 ppm when the data are compared to

those of 3a–f. These observations are consistent with those for

comparable Pt(ii) (poly)fluorido complexes.[12]

Note that for 2a–fonly broad signals with 195Pt satellites

were detected in the 19F NMR spectra at 30°C and cooling to

70°C or 90°C did not resolve any additional coupling

(Figure 2, bottom). The absolute values of the (negative, see

below) j1J(F,Pt)jcoupling constants in the polyfluorido com-

plexes 2a–fare larger (639–569 Hz) when compared to these

for the fluorido complexes 3a–f(515-567 Hz). An increase of

the absolute values of the j1J(F,Pt)jcoupling constants upon

coordination of HF was also observed for the fluorido com-

plexes cis-[Pt(F){k2-(P,N)-iPr2P(C9H7N)}{iPr2P(Ind)}][7] and trans[Pt-

(F)(CH3){R2P(Ind)}2] (R=Ph, 4-FC6H4, 4-CF3C6H4).[12]

The 31P{1H} NMR spectra of 3a–fand 2 a–feach disclose a

doublet with 195Pt satellites, due to coupling of the two

phosphorus nuclei to the fluorido ligand. The 1J(P,Pt) coupling

constants of 3a–fand 2a–freveal typical values for Pt(ii)

complexes bearing a carbon bound σ-donor ligand and two

phosphine ligands in a mutually trans coordination.[12,24, 29]

The IR spectra of the fluorido complexes 2a–fand 3a–f

featured broad absorption bands below 3100 cm1, which can

be assigned to the NH···F moieties. Note, that absorptions of

N-H hydrogen bonded fluorides have been reported in a region

between 3000–3150 cm1.[30] However, due to overlapping with

CH absorption bands, no distinct band maxima could be

determined. For 2a–fbroad features were detected in the

regions of 2700-2500 cm1and at around 1800 cm1, which are

typical bands for polyfluoride moieties.[30–31]

Overall, the NMR data of the complexes 2a–fand 3 a–f

reveal several interesting trends. The 1J(P,Pt) coupling constants

decrease continuously in the series from 2a to 2f as well as 3a

to 3f from 3164 Hz to 3080 Hz and 3176 Hz to 3090 Hz,

respectively. As only the substituent in the para-position of the

aryl ligand differs, this corresponds to a larger cis-influence of

the aryl ligands featuring electron withdrawing substituents,

weakening somewhat the PtP bonds.[15,32] Indeed, analysis of

the DFT optimised structures for 2a-f and 3a-f reveals a

successive lengthening of the average PtP bonds with

increasing electronegativity of the substituent in the para-

position of the aryl ligand. The computed 1J(P,Pt) couplings for

3a–f(Tables S3, S4 in Supporting Information) do not show an

as clear trend, but with (at least) one HF molecule hydrogen-

bonded to the fluoride, the distinction between electron-

donating substituents (3a–3c) and electron-withdrawing ones

(3d–3f) becomes clearer, as it does for 2a–2f (Tables S3, S4),

i.e. with two HF molecules present. Similar to the effect of HF

coordination, explicit hydrogen-bonding by two CH2Cl2solvent

molecules leads to an increase of the 1J(P,Pt) couplings,

although to a lesser extent (excluding 3a·(CH2Cl2)2from the

analysis). Overall, the cis influence of the aryl ligands follows the

order: 4-tBuC6H4(a)�4-CH3C6H4(b)<Ph (c)!4-FC6H4(d)<4-

ClC6H4(e)<4-CF3C6H4(f). This trend is inverse to the trans

influence of the aryl ligands observed for 1a–f, which is also

consistent with the literature.[15,32]

Furthermore, the NHchemical shift in the 1H NMR spectra as

well as 1J(H,F) coupling constants suggest a weakening of the

NH···F hydrogen bond by additional fluoride bound HF mole-

cules in the polyfluorido complexes 2a–f. However, the

absolute values of j1J(F,Pt)jcoupling constants are larger for

the polyfluorido complexes 2a–fthan for the fluorido com-

plexes 3a–f. In addition, decreasing 1J(P,Pt) coupling constants

for the sequences 2a to 2f as well as for 3a to 3f correlate with

high-frequency shifts of the signal for the fluorido ligand and

smaller j1J(F,Pt)jcoupling constant in the 19F NMR spectra; i.e.

more electronegative aryl ligands show smaller j1J(F,Pt)j

couplings.

For the j1J(F,Pt)jcoupling constants of the fluorido com-

plexes 3a–fit is important to note that the computations show

them to have negative signs (Table S3, S4). This is consistent

with the smaller fluorine s-character in the FPt bond compared

to phosphorus and similar to, for example, 1J(CF) couplings.[34]

As for the j1J(F,Pt)jcoupling constants, the computations give

overall negative couplings at the given BHLYP DFT level, even

more so when including two CH2Cl2solvent molecules hydro-

gen-bonded to the platinum-bound fluorine. Assuming a

negative sign, the experimental data indicate less negative

1J(F,Pt) values in the series 3 a (567 Hz) to 3f (515 Hz). Again,

the calculations on non-solvated 3a–3 f do not capture the

trend correctly, while computations with explicit microsolvation

by two CH2Cl2molecules distinguish between more negative

couplings for 3a–3c and less negative ones for 3d-3f

(Tables S3, S4). However, then the absolute values are over-

Figure 2. Sections of the 19F NMR NMR spectra of 2 a (bottom) and 3a (top),

revealing coupling constants of j1J(F,Pt)j=639 Hz for 2 a and 1J(F,H)=50 Hz,

2J(F,P)=13 Hz, j1J(F,Pt)j=567 Hz for 3a.

Chemistry—A European Journal

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estimated, even more when for 2 a–2f (Tables S3, S4). Therefore,

we have to assume that the systematic DFT error can be about

200 Hz to 300 Hz. Computationally, the trans influence is

clearly to some extent coupled to all the inter- and intra-

molecular hydrogen bonds present, rendering NMR analyses

more complex. One complication for 3a–3f is obviously due to

charge-assisted CH···F hydrogen bonds to the CH2Cl2solvent

(see above). Some of us have recently analyzed such inter-

actions in detail using similar microsolvated cluster models[35]

and found them to be substantial whenever NPA charges that

are more negative than 0.6 on fluorine are present. This is

clearly the case for the platinum fluorides studied here

(Tables S1, S2). The various hydrogen-bonding interactions

likely also prevent a more accurate representation of the subtle

substituent effects for the present systems. In the case of 2a–2f

our modelling includes two explicit HF molecules (Tables S3,

S4). In solution we have to expect, however, that these HF

molecules are also microsolvated by CH···F hydrogen bonding

with CH2Cl2, generating further complications.

Overall, more hydrogen bonding to the Pt-bound fluoride,

either by HF or by the CH2Cl2solvent, clearly provides more

negative j1J(F,Pt)jcouplings, even though the magnitudes are

not easy to reproduce computationally. This is consistent with

experimental observations for the fluorido methyl complex

trans-[Pt(F)(CH3)(Ph3P)2], which does not exhibit any hydrogen

bonding to the fluorido ligand and which exhibits a j1J(F,Pt)j

coupling constant of 361 Hz that is lowered by 150–200 Hz

compared to 3a–f. On the other hand, the methyl fluorido

complex trans-[Pt(F)(CH3){Ph2P(Ind)}2], featuring hydrogen bond-

ing from indolylphosphine ligands to the fluorido ligand,

exhibits a j1J(F,Pt)jcoupling constant of 546 Hz that is

comparable with those found for 3a–f.[12,36]

Furthermore, the molecular structures of 3a,3 c and 3d

were determined by single crystal X-ray diffraction (Figure 3,

Table 3). In all cases electron density which could be assigned

to nitrogen bound hydrogen atoms were found in the differ-

ence Fourier map and a free refinement was allowed. For

complex 3d, the molecule is located on a mirror plane and the

asymmetric unit consists only of one half of the molecule. All

structures reveal a slightly distorted square-planar coordination

of the ligands, with the two phosphine ligands in a mutually

trans position, exhibiting hydrogen bonds from their indolyl NH

groups to the fluorido ligand. The PtP bond lengths of 3 a

(2.3124(4), 2.3220(4) Å) and 3c (2.3118(5), 2.3188(6) Å) are

slightly shorter than those of 3d (2.3254(7) Å), which is in

accordance with the trend of the observed 1J(P,Pt) coupling

constants.[13d] Generally, all PtP bond lengths are in accordance

with similar data for Pt(ii) fluorido complexes reported

previously.[1d,12]

The PtF bond lengths of 3a (2.1361(9) Å) and 3c

(2.1386(13) Å) are slightly longer compared to 3d (2.125(3) Å)

which might result from the larger trans influence of the 4-tBu

and Ph ligands, respectively. However, all PtF bond lengths

are elongated compared to Pt(ii) fluorido complexes that

feature no hydrogen bonding to the fluorido ligand in the

coordination sphere (1.9787(14)-2.117(3) Å).[1d,e,4d,5g,k] A PtF

bond length of 2.1466(13) Å was observed for the molecular

structure of the fluorido complex trans-[Pt(F)(CH3){(4-FC6H4)2P-

(Ind)}2] that also features indolylphosphine ligands.[12] The N···F

distances of 3a (2.591(1), 2.610(1) Å), 3c (2.620(3), 2.619(2) Å)

and 3d (2.588 Å) suggest hydrogen bonding of medium

strength to the fluorido ligand.[10b,12,37] The FPtPN dihedral

angles of 3a and 3c reveal relative small values of 12.89(4)°

and 19.86(4)°as well as 18.31(6)°and 19.06(6)°, respectively,

resulting in a favoured alignment of the NH···F bond. The

indolyl moieties in 3d appear to be more twisted, expressed by

a larger dihedral FPtPN angle of 28.72°. This might be due

to crystal packing effects associated with short contact inter-

actions of a proximal CH group of a 4-fluorophenyl ligand to

the fluorido ligand of a second molecule, as well as CH-π-

interactions between phosphine ligands. However, all fluorido

complexes 3a,3c and 3d reveal smaller dihedral FPtPN

angles when compared to the ClPtPN angles of the chlorido

analogue trans-[Pt(Cl)(Ph){Ph2P(Ind)}2] (4) (Cl1-Pt1-P1-N1

61.94(4)°, Cl1-Pt1-P2-N2 51.37(4)°), which is very likely explained

by the sterically more demanding chlorido ligand (Figure 4).

Figure 3. Molecular structures of trans-[Pt(F)(4-tBuC6H4){Ph2P(Ind)}2] (3a) (left), trans-[Pt(F)(Ph){Ph2P(Ind)}2] (3c) (middle) and trans-[Pt(F)(4-FC6H4){Ph2P(Ind)}2]

(3d) (right). Thermal ellipsoids are drawn at 50% probability level, the intermolecular hydrogen bonds are depicted as magenta dashed lines. Carbon bound

hydrogen atoms and the solvent molecules were omitted for clarity.

Chemistry—A European Journal

Research Article

doi.org/10.1002/chem.202202768

Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 110/116] 1

Both NHgroups of the indolyl moieties form hydrogen bonds

to the chlorido ligand with typical N···Cl distances of 3.241(2) Å

and 3.168(2) Å.[7,29,38] Complex 4was synthesised by treatment

of [Pt(Cl)(Ph)(COD)] with Ph2P(Ind).

Conclusion

In conclusion, we describe the formation of the platinum

fluorido and polyfluorido complexes trans-[Pt(F)(Ar){Ph2P(Ind)}2]

3a-f and trans-[Pt(F·(HF)2)(Ar){Ph2P(Ind)}2]2a-f bearing elec-

tronically different aryl ligands (Ar=4-tBuC6H4(1a),4-CH3C6H4

(1b), Ph (1c), 4-FC6H4(1d), 4-ClC6H4(1e), 4-CF3C6H4(1f)), as well

as 2-(3-methyl)indolyl (Ind) substituted phosphine ligands that

allow for generation of intramolecular hydrogen bonding to the

platinum bound fluoride. The complexes were analysed thor-

oughly by multinuclear NMR spectroscopy and in part by single

crystal X-ray diffraction. X-ray data revealed a lower trans

influence for aryl ligands with electron withdrawing substitu-

ents in the para position, but simultaneously a larger cis

influence was observed. The cis influence was mirrored by the

NMR 1J(P,Pt) coupling constants,[15] whereas the trans influence

is not mirrored by the j1J(F,Pt)jcoupling constants. In addition,

the j1J(F,Pt)jcoupling constants were found to be smaller for

fluorido complexes 3a–fcompared to polyfluorido complexes

2a–f. Moreover, intramolecular hydrogen bonding of the

fluorido ligand to the indolyl NHmoiety seems to be slightly

weaker in the polyfluorido systems 2a–fbased on NHchemical

shifts and 1J(H,F) coupling constants. DFT calculations suggest

that, due to the high negative charge on the platinum-bound

fluoride, hydrogen bonding by HF, but also by the dichloro-

methane solvent molecules to the fluoride have a considerable

influence on the NMR parameters, complicating their quantita-

tive description by DFT methods.

Table 3. Selected bond lengths, distances [Å] and bond angles [°] of 3a,3c and 3d.

complex Pt1-P1

Pt1-P2

Pt1-F1 Pt1-C(Aryl) N1···F1

N2···F1

P1-Pt1-F1

P2-Pt1-F1

P1-Pt1-P2(P1’)

F1-Pt1-C(Aryl)

P1-Pt1-C(Aryl)

P2-Pt1-C(Aryl)

N1-H1···F1

N2-H2···F1

F1-Pt1-P1-N1

F1-Pt1-P2-N2

3a 2.3124(4)

2.3220(4)

2.1361(9) 1.9990(14) 2.591(1)

2.610(1)

93.23(3)

93.89(3)

171.165(12)

178.06(4)

86.27(4)

160(2)

152(3) 12.89(4)

19.86(4)

3c 2.3118(5)

2.3188(6)

2.1386(13) 2.012(2) 2.620(3)

2.619(2)

92.23(4)

93.94(4)

173.614(19)

177.00(8)

87.21(6)

86.71(6)

158(3)

164(3)

18.31(6)

19.06(6)

3d 2.3254(7)

–

2.125(3) 1.991(5) 2.588

–

92.10(2)

–

174.97(4)

175.45(15)

88.01(2)

–

160

–

28.72

–

Figure 4. Molecular structure of trans-[Pt(Cl)(Ph){Ph2P(Ind)}2] (4). Thermal

ellipsoids are drawn at 50% probability level, the intermolecular hydrogen

bond is depicted as a magenta dashed line. Carbon bound hydrogen atoms

and the solvent molecule were omitted for clarity. Selected bond lengths,

distances [Å] and bond angles [°]: Pt1-P1 2.2978(5), Pt1-P2 2.2960(5), Pt1-Cl1

2.4314(6), Pt1-C43 2.0219(18), N1···Cl1 3.241(2), N2···Cl1 3.168(2), P1-Pt1-Cl1

87.740(18), P2-Pt1-Cl1 89.154(19), P1-Pt1-P2 169.154(16), P1-Pt1-C1 90.55(5),

P2-Pt1-C1 92.96(5), Cl1-Pt1-C1 177.05(5), N1-H1···Cl1 147(2), N2-H2···Cl1

147(2), Cl1-Pt1-P1-N1 61.94(4), Cl1-Pt1-P2-N2 51.37(4).

Chemistry—A European Journal

Research Article

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Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 111/116] 1

Experimental Section

All manipulations (if not otherwise mentioned) were carried out

under argon using standard Schlenk techniques or in an argon-

filled glovebox (MBRAUN). THF and n-hexane were dried and

purified by distillation from SOLVONA® and stored under argon

over molecular sieves. n-Pentane was purified using a two-column

solid-state purification system (MBRAUN). Dichloromethane and

CD2Cl2were purified by distillation from CaH2and stored over

molecular sieves. [Pt(Cl)(CH3)(COD)][19] and Ph2P(Ind)[39] were pre-

pared according to the literature.

Poly[4-vinylpyridinium poly(hydrogen fluoride)] (PVPHF; 38–42 wt%

HF) and 1-bromo-4-tert-butylbenzene were obtained from Sigma-

Aldrich and were used without further purification. 4-Bromobenzo-

trifluoride was obtained from abcr GmbH and was used without

further purification. p-Tolylmagnesium bromide (0.5 M in Et2O),

phenylmagnesium bromide (1.6 M in cyclopentyl methyl ether), 4-

fluorophenylmagnesium bromide (2 M in Et2O) and 4-chlorophenyl-

magnesium bromide (1 M in THF/toluene) were obtained from

Acros Organics. The NMR spectra were recorded on a Bruker Avance

500, Bruker Avance 400, Bruker Avance 300, or a Bruker DPX 300

spectrometer. The 1H NMR chemical shifts were referenced to

residual CDHCl2at δ=5.32 ppm. The 13C{1H} NMR spectra were

referenced to CD2Cl2at δ=54.00 ppm. The 15N NMR chemical shifts

were referenced to external CH3NO2at δ=0.00 ppm. The 19F NMR

chemical shifts were referenced to external CFCl3at δ=0.00 ppm.

The 31P{1H} NMR chemical shifts were referenced to external H3PO4

at δ=0.00 ppm.

Structure determination of complexes 1d, 1e, 3a, 3c, and 3d:

Colourless crystals of 1d·0.5CH2Cl2,1e,3a·CH2Cl2,3c·0.5 CH2Cl2

and 3d were obtained by slow evaporation of the solvent from a

dichloromethane solution at room temperature. The diffraction

data were collected at a Bruker D8 Venture diffractometer at 100 K

using Mo-Kα(λ=0.71073 Å) radiation. Multi-scan absorption correc-

tions implemented SADABS were applied to the data.[40] The

structures were solved by intrinsic phasing method (SHELXT

2014/5)[41] and refined by full-matrix least-squares methods on F2

(SHELXL 2016/4 or SHELXL-2018/3).[42] The nitrogen-bound hydro-

gen atoms were found in the difference electron density maps and

freely refined. All other hydrogen atoms were placed at calculated

positions and refined using a riding model.

Deposition Number(s) 2166083 (for 1d·0.5 CH2Cl2), 2166086 (for

1e), 2166098 (for 3 a·CH2Cl2), 2166090 (for 3c·0.5 CH2Cl2), 2166111

(for 3d) and 2170875 (for 4) contain(s) the supplementary crystallo-

graphic data for this paper. These data are provided free of charge

by the joint Cambridge Crystallographic Data Centre and Fachinfor-

mationszentrum Karlsruhe Access Structures service.

General procedure for the synthesis of [Pt(Ar)(CH3)(COD)] (Ar=4-

tBuC6H4, 4-CH3C6H4,[16] Ph,[17] 4-FC6H4,[18] 4-ClC6H4, 4-CF3C6H4): The

reactions were carried out under Argon, but the work-ups were

done under air. In a Schlenk flask [PtCl(CH3)(COD)] (0.71 g,

2.00 mmol) was dissolved in dry CH2Cl2(20 mL) and solution was

cooled to 0°C followed by dropwise addition of the appropriate

Grignard reagent ArMgBr (4.40 mmol) (Ar=4-tBuC6H4, 4-CH3C6H4,

Ph, 4-FC6H4, 4-ClC6H4, 4-CF3C6H4). The reaction mixture was stirred

for 30 min and then cooled to 78°C. 2-Propanol (2 mL) was added

to quench excess of the Grignard. The mixture was allowed to

warm up to room temperature. Water was added (50 mL) and the

mixture was stirred vigorously for 5 min. The two phases were

allowed to separate and the lower organic phase was collected. The

aqueous phase was extracted with dichloromethane (2×25 mL).

The combined organic phases were washed with water (2×50 mL)

and dried over anhydrous MgSO4. After filtration, all volatiles were

removed in vacuo yielding pale yellow to brownish solids. Potential

brownish-dark colouring of the solids can be removed by filtration

over a pad of silica or Florisil®. The obtained solids were finally

washed with small portions of cold n-pentane and dried in vacuo to

give [Pt(Ar)(CH3)(COD)] as colourless or off-white solids. The

complexes obtained by this way can be used without further

purification. Yields: 84–94%.

Analytical data for [Pt(4-tBuC6H4)(CH3)(COD)]:1H NMR (300.1 MHz,

CD2Cl2): δ=7.31–7.05 (m, 4H, ArH), 6.91 (m, 2H, ArH), 5.09 (m+sat,

2J(H,Pt)=39 Hz, 2H, CH), 4.83 (m+sat., 2J(H, Pt=39 Hz, 2H, CH), 2.43

(m, 8H, CH2), 1.29 (s, 9H, C(CH3)3), 0.78 ppm (s+sat., 2J(H, Pt)=

83 Hz, 3H, Pt-CH3). 13C{1H} NMR (75.4 MHz, CD2Cl2): δ=155.1 (s+sat,

J(C,Pt)=1097 Hz, Pt-Car), 145.6 (s+sat., J(C,Pt)=13 Hz, Car), 134.8 (s

+sat., J(C,Pt)=38 Hz, CarH), 125.1 (s+sat, J(C,Pt)=76 Hz, CarH),

102.7 (s+sat., J(C,Pt)=50 Hz, CH), 102.2 (s+sat., J(C,Pt)=52 Hz,

CH), 34.4 (s, C(CH3)3), 31.8 (s, C(CH3)3), 30.7 (s, CH2), 30.2 (s, CH2), 21.1

(s, CH3), 6.9 (s+sat., J(C,Pt)=778 Hz, Pt-CH3). Anal. Calcd for

C19H28Pt: C, 50.54; H, 6.25. Found: C, 50.66; H, 6.28.

Analytical data for [Pt(4-CH3C6H4)(CH3)(COD)][16]:1H NMR

(300.1 MHz, CD2Cl2): δ=7.13 (m+sat, 2J(H,Pt)=68 Hz, 2H, ArH), 6.91

(m, 2H, ArH), 5.07 (m+sat, 2J(H,Pt)=39 Hz, 2H, CH), 4.79 (m+sat.,

2J(H, Pt=39 Hz, 2H, CH), 2.41 (m, 8H, CH2), 0.75 ppm (s+sat., 2J(H,

Pt)=83 Hz, 3H, Pt-CH3). 13C{1H} NMR (75.4 MHz, CD2Cl2): δ=155.0 (s

+sat, J(C,Pt)=1097 Hz, Pt-Car), 135.0 (s+sat., J(C,Pt)=38 Hz, CarH),

132.2 (s+sat., J(C,Pt)=13 Hz, Car), 129.0 (s+sat, J(C,Pt)=77 Hz,

CarH), 102.7 (s+sat., J(C,Pt)=50 Hz, CH), 102.3 (s+sat., J(C,Pt)=

52 Hz, CH), 30.7 (s, CH2), 30.2 (s, CH2), 21.1 (s, CH3), 6.8 (s+sat.,

J(C,Pt)=778 Hz, Pt-CH3).

Analytical data for [Pt(Ph)(CH3)(COD)][17]:1H NMR (300.1 MHz,

CD2Cl2): δ=7.24 (m+sat, 2H, 2J(H,Pt)=68 Hz, ArH), 7.05 (m, 2H,

ArH), 6.85 (m, 1H, ArH), 5.09 (m+sat, 2J(H,Pt)=40 Hz, 2H, CH), 4.80

(m+sat., 2J(H, Pt=39 Hz, 2H, CH), 2.43 (m, 8H, CH2), 0.76 ppm (s+

sat., 2J(H, Pt)=83 Hz, 3H, Pt-CH3). 13C{1H} NMR (75.4 MHz, CDCl3): δ=

158.5 (s+sat, J(C,Pt)=1094 Hz, Pt-Car), 134.9 (s+sat., J(C,Pt)=36 Hz,

CarH), 127.8 (s+sat, J(C,Pt)=76 Hz, CarH), 122.9 (s+sat., J(C,Pt)=

12 Hz, Car), 102.1 (s+sat., J(C,Pt)=50 Hz, CH), 101.7 (s+sat., J(C,Pt)-

=51 Hz, CH), 30.2 (s, CH2), 29.8 (s, CH2), 6.8 (s+sat., J(C,Pt)=772 Hz,

Pt-CH3).

Analytical data for [Pt(4-FC6H4)(CH3)(COD)][18]:1H NMR (500.1 MHz,

CD2Cl2): δ=7.23 (m+sat, 2H, 2J(H,Pt)=68 Hz, ArH), 6.84 (m, 2H,

ArH), 5.09 (m+sat, 2J(H,Pt)=40 Hz, 2H, CH), 4.79 (m+sat., 2J(H, Pt=

39 Hz, 2H, CH), 2.43 (m, 8H, CH2), 0.77 ppm (s+sat., 2J(H, Pt)=82 Hz,

3H, Pt-CH3). 13C{1H} NMR (125.8 MHz, CD2Cl2): δ=160.5 (d+sat.,

J(C,F)=239.0 Hz, J(C,Pt)=17 Hz, Car-F), 153.3 (d+sat, J(C,F)=3.5 Hz,

J(C,Pt)=1112 Hz, Pt-Car), 135.7 (d+sat., J(C,F)=5.5 Hz, J(C,Pt)=

44 Hz, CarH), 114.6 (d+sat., J(C,F)=18.2 Hz, J(C,Pt)=84 Hz, CarH),

102.7 (s+sat., J(C,Pt)=52 Hz, CH), 30.7 (s, CH2), 30.3 (s, CH2), 6.6 (s+

sat., J(C,Pt)=768 Hz, Pt-CH3). 19F{1H} NMR (470.6 MHz, CD2Cl2): δ=

123.4 ppm (s+sat., 5J(F, Pt)=26 Hz, Ar-F).

Analytical data for [Pt(4-ClC6H4)(CH3)(COD)]:1H NMR (300.1 MHz,

CD2Cl2): δ=7.22 (m+sat, 2J(H,Pt)=67 Hz, 2H, ArH), 7.05 (m, 2H,

ArH), 5.09 (m+sat, 2J(H,Pt)=40 Hz, 2H, CH), 4.77 (m+sat., 2J(H, Pt=

38 Hz, 2H, CH), 2.43 (m, 8H, CH2), 0.74 ppm (s+sat., 2J(H, Pt)=82 Hz,

3H, Pt-CH3). 13C{1H} NMR (75.4 MHz, CD2Cl2): δ=157.4 (s+sat,

J(C,Pt)=1110 Hz, Pt-Car), 136.4 (s+sat., J(C,Pt)=42 Hz, CarH), 128.7

(s+sat., J(C,Pt)=17 Hz, Car), 127.9 (s+sat, J(C,Pt)=82 Hz, CarH),

103.0 (s+sat., J(C,Pt)=53 Hz, CH), 102.7 (s+sat., J(C,Pt)=51 Hz,

CH), 30.6 (s, CH2), 30.3 (s, CH2), 6.3 (s+sat., J(C,Pt)=765 Hz, Pt-CH3).

Anal. Calcd for C15H19ClPt: C, 41.91; H, 4.46. Found: C, 41.96; H, 4.47.

Analytical data for [Pt(4-CF3C6H4)(CH3)(COD)]:1H NMR (300.1 MHz,

CD2Cl2): δ=7.42 (m+sat, 2J(H,Pt)=68 Hz, 2H, ArH), 7.29 (m, 2H,

ArH), 5.14 (m+sat, 2J(H,Pt)=40 Hz, 2H, CH), 4.78 (m+sat., 2J(H, Pt=

38 Hz, 2H, CH), 2.44 (m, 8H, CH2), 0.74 ppm (s+sat., 2J(H, Pt)=82 Hz,

3H, Pt-CH3). 13C{1H} NMR (75.4 MHz, CD2Cl2): δ=165.8 (s+sat,

Chemistry—A European Journal

Research Article

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Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 112/116] 1

J(C,Pt)=1106 Hz, Pt-Car), 135.6 (s+sat., J(C,Pt)=39 Hz, CarH), 125.7

(q, J(C,F)=271.1 Hz, CF3), 124.9 (q, J(C,F)=31.6 Hz, CarH), 124.1 (q+

sat, J(C,F)=3.8 Hz, J(C,Pt)=79 Hz), 103.5 (s+sat., J(C,Pt)=53 Hz,

CH), 102.8 (s+sat., J(C,Pt)=51 Hz, CH), 30.7 (s, CH2), 30.3 (s, CH2), 5.9

(s+sat., J(C,Pt)=761 Hz, Pt-CH3). 19F NMR (470.6 MHz, CD2Cl2): δ=

62.4 ppm (CF3). Anal. Calcd for C16H19F3Pt: C, 41.47; H, 4.13. Found:

C, 41.62; H, 4.24.

Synthesis of cis-[Pt(Me)(4-tBuC6H4){PPh2(Ind)}2] (1a): A solution of

diphenyl-2-(3-methyl)indolylphosphine (662 mg, 2.10 mmol) in

CH2Cl2(10 mL) was added to a solution of [Pt(4-tBuC6H4)(CH3)(COD)]

(452 mg, 1.00 mmol) in CH2Cl2(10 mL) while stirring. The resulting

solution was stirred for another hour. The solvent was then

removed in vacuo to yield an off-white solid. The crude product

was washed with pentane (5×5 mL) and the solid was dried in

vacuo, affording 1a as a colourless powder. Yield 737 mg (76%). IR

(ATR, diamond): ~

v=3445 cm1(medium, broad, NH), 3365 cm1

(medium, broad, NH). 1H NMR (400.1 MHz, CD2Cl2): δ=9.02 (s, 1H,

NH), 8.52 (s, 1H, NH), 7.58 (d, 3J(H,H)=7.9 Hz, 1H, ArH), 7.45 (d,

3J(H,H)=7.7 Hz, 1H, ArH), 7.41 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 7.31 (dd,

3J(H,H)=8.2 Hz, 3J(H,H)=6.9 Hz, 1H ArH), 7.23 (m, 3H, ArH), 7.17 (m,

4H, ArH), 7.11-7.02 (m, 14H, ArH), 6.96 (m, 4H, ArH), 6.72 (d,

3J(H,H)=8.3 Hz, 2H, ArH), 6.68 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 2.03 (s,

3H, ArCH3), 1.90 (s, 3H, ArCH3), 1.17 (s, 9H, C(CH3)3), 0.49 (m+sat.,

2J(H,Pt)=68 Hz, 3H, Pt-CH3). 31P{1H} NMR (162.0 MHz, CD2Cl2): δ=9.3

(d+sat., 2J(P,P)=9.8 Hz, 1J(Pt,P)=1594 Hz), 9.1 ppm (d+sat., 2J-

(P,P)=9.8 Hz, 1J(Pt,P)=1898 Hz). Anal. Calcd for C50H46N2P2Pt: N,

2.88; C, 65.35; H, 5.38. Found: N, 2.89; C, 65.55; H, 5.34.

Synthesis of cis-[Pt(Me)(4-MeC6H4){PPh2(Ind)}2] (1b): A solution of

diphenyl-2-(3-methyl)indolylphosphine (687 mg, 2.18 mmol) in

CH2Cl2(10 mL) was added to a solution of [Pt(4-CH3C6H4)(CH3)(COD)]

(446 mg, 1.09 mmol) in CH2Cl2(10 mL) while stirring. The resulting

solution was stirred for another hour. The solvent was then

removed in vacuo to yield an off-white solid. The crude product

was washed with pentane (5×5 mL) and the solid was dried in

vacuo, affording 1b as a colourless powder. Yield 873 mg (86%). IR

(ATR, diamond): ~

v=3449 cm1(medium, broad, NH), 3370 cm1

(medium, broad, NH). 1H NMR (400.1 MHz, CD2Cl2): δ=8.99 (s, 1H,

NH), 8.48 (s, 1H, NH), 7.59 (d, 3J(H,H)=7.9 Hz, 1H, ArH), 7.45 (d,

3J(H,H)=8.1 Hz, 1H, ArH), 7.40 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 7.30 (m,

1H, ArH), 7.21 (m, 7H, ArH), 7.13 (m, 7H, ArH), 7.05 (m, 7H, ArH), 6.97

(m, 4H, ArH), 6.71 (d, 3J(H,H)=7.9 Hz, 1H, ArH), 6.54 (d, 3J(H,H)=

7.2 Hz, 2H, ArH), 2.07 (s, 3H, ArCH3), 1.97 (d, 4J(H,P)=1.2 Hz, 3H,

ArCH3), 1.92 (d, 4J(H,P)=1.3 Hz, 3H, ArCH3), 0.50 ppm (dd+sat.,

3J(H,P)=9.6 Hz, 3J(H,P)=6.5 Hz, 2J(Pt,H)=68 Hz, 3H, CH3). 31P{1H}

NMR (162.0 MHz, CD2Cl2): δ=9.4 (d+sat., 2J(P,P)=9.8 Hz, 1J(Pt,P)=

1615 Hz), 8.6 ppm (d+sat., 2J(P,P)=9.8 Hz, 1J(Pt,P)=1888 Hz). Anal.

Calcd for C50H46N2P2Pt: N, 3.01; C, 64.44; H, 4.98. Found: N, 2.89; C,

64.27; H, 5.20.

cis-[Pt(CH3)(Ph){PPh2(Ind)}2] (1c): A solution of diphenyl-2-(3-meth-

yl)indolylphosphine (1.24 g, 3.92 mmol) in CH2Cl2(20 mL) was

added to solution of [Pt(Ph)(CH3)(COD)] (0.74 g, 1.87 mmol) in

CH2Cl2(15 mL) while stirring. The resulting solution was stirred for

another hour. The solvent was then removed in vacuo yielding the

crude product as an off-white solid which was recrystallised from

CH2Cl2/n-hexane (5 mL/60 mL) at 0°C. The solid was collected by

filtration, washed with n-pentane (3×5 mL) and dried in vacuo to

yield 1c as a colourless powder. Yield 1.33 g (77%). IR (ATR,

diamond): ~

v=3444 cm1(medium, broad, NH), 3363 cm1(me-

dium, broad, NH). 1H NMR (400.1 MHz, CD2Cl2): δ=8.98 (br s, 1H,

NH), 8.50 (br s, 1H, NH), 7.58 (d, 3J(H,H)=8.0 Hz, 1H, ArH), 7.46 (d,

3J(H,H)=7.2 Hz, 1H, ArH), 7.40 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 7.30 (m,

1H, ArH), 7.23 (m, 5H, ArH), 7.17 (m, 4H, ArH), 7.11 (m, 7H, ArH), 7.05

(m, 5H, ArH), 6.97 (m, 4H, ArH), 6.69 (m, 3H, ArH), 6.54 (m, 1H, ArH),

2.02 (d, 4J(H,P)=1.1 Hz, 3H, ArCH3), 1.91 (d, 4J(P,H)=1.1 Hz, 3H,

ArCH3), 0.51 ppm (dd+sat., 3J(H,P)=9.3 Hz, 3J(H,P)=6.5 Hz, 2J(H,Pt)-

=68 Hz, 3H, CH3). 31P{1H} NMR (162.0 MHz, CD2Cl2): δ=9.1 (d+sat.,

2J(P,P)=9.9 Hz, 1J(P,Pt)=1607 Hz), 9.1 ppm (d+sat., 2J(P,P)=9.9 Hz,

1J(P,Pt)=1891 Hz). Anal. Calcd for C49H44N2P2Pt: N, 3.05; C, 64.12; H,

4.83. Found: N, 2.77; C, 63.75; H, 5.14.

Synthesis of cis-[Pt(Me)(4-ClC6H4){PPh2(Ind)}2] (1e): A solution of

diphenyl-2-(3-methyl)indolylphosphine (659 mg, 2.09 mmol) in

CH2Cl2(10 mL) was added to a solution of [Pt(4-ClC6H4)(CH3)(COD)]

(451 mg, 1.05 mmol) in CH2Cl2(10 mL) while stirring. The resulting

pink solution was stirred for another hour. The solvent was then

removed in vacuo to yield an off-white solid. The crude product

was washed with pentane (5×5 mL) and the solid was dried in

vacuo, affording 1e as a colourless powder. Yield 950 mg (95%). IR

(ATR, diamond): ~

v=3444 cm1(medium, broad, NH), 3368 cm1

(medium, broad, NH). 1H NMR (400.1 MHz, CD2Cl2): δ=8.90 (s, 1H,

NH), 8.47 (s, 1H, NH), 7.59 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 7.48 (d,

3J(H,H)=7.5 Hz, 1H, ArH), 7.39 (d, 3J(H,H)=8.2 Hz, 1H, ArH), 7.31 (m,

1H, ArH), 7.26-6.97 (m, 25H, ArH), 6.70 (d, 3J(H,H)=7.7 Hz, 1H, ArH),

6.64 (m, 2H, ArH), 2.10 (d, 4J(H,P)=1.2 Hz 3H, ArCH3), 1.94 (d,

4J(P,H)=1.2 Hz, 3H, ArCH3), 0.49 ppm (dd+sat., 3J(H,P)=9.3 Hz,

3J(H,P)=6.4 Hz, 2J(H,Pt)=68 Hz, 3H, CH3). 31P{1H} NMR (162.0 MHz,

CD2Cl2): δ=9.0 (d+sat., 2J(P,P)=10.5 Hz, 1J(P,Pt)=1670 Hz),

8.8 ppm (d+sat., 2J(P,P)=10.5 Hz, 1J(P,Pt)=1870 Hz). Anal. Calcd

for C49H43ClN2P2Pt: N, 2.94; C, 61.80; H, 4.55. Found: N, 2.75; C, 61.55;

H, 4.70.

Synthesis of cis-[Pt(Me)(4-CF3C6H4){PPh2(Ind)}2] (1f): A solution of

diphenyl-2-(3-methyl)indolylphosphine (306 mg, 0.97 mmol) in

CH2Cl2(5 mL) was added to a solution of [Pt(4-CF3C6H4)(CH3)(COD)]

(227 mg, 0.49 mmol) in CH2Cl2(5 mL) while stirring. The resulting

solution was stirred for another hour. The solvent was then

removed in vacuo to yield the crude product as a yellow powder.

This was washed with pentane (5×5 mL) and dried in vacuo to yield

1f as a pale-yellow powder. Yield 338 mg (70%). IR (ATR, diamond):

v=3449 cm1(medium, broad, NH), 3370 cm-1 (medium, broad,

NH). 1H NMR (400.1 MHz, CD2Cl2): δ=8.88 (s, 1H, NH), 8.45 (s, 1H,

NH), 7.60 (d, 3J(H,H)=7.8 Hz, 1H, ArH), 7.48 (m, 3J(H,H)=8.5 Hz, 1H,

ArH), 7.40 (m, 3J(H,H)=8.2 Hz, 1H, ArH), 7.34-7.17 (m, 10H, ArH),

7.08 (m, 12H, ArH), 6.97 (m, 4H, ArH), 6.86 (d, 3J(H,H)=7.6 Hz, 2H,

ArH), 6.69 (m, 1H, ArH), 2.14 (d, 4J(H,P)=1.3 Hz, 3H, ArCH3), 1.95 (d,

4J(H,P)=1.3 Hz, 3H, ArCH3), 0.51 (dd+sat., 3J(H,P)=9.2 Hz, 3J(H,P)=

6.3 Hz, 2J(H,Pt)=67 Hz, 3H, CH3). 19F NMR (282.4 MHz, CD2Cl2): δ=

62.2 ppm (s, CF3). 31P{1H} NMR (162.0 MHz, CD2Cl2): δ=9.1 (d+

sat., 2J(P,P)=11.0 Hz, 1J(P,Pt)=1877 Hz), 8.77 ppm (d+sat., 2J(P,P)=

11.0 Hz, 1J(P,Pt)=1669 Hz). Anal. Calcd for C50H43F3N2P2Pt: N, 2.84; C,

60.91; H, 4.40. Found: N, 2.63; C, 60.70; H, 4.71.

General procedure for the formation of fluorido complexes trans-

[Pt(F·(HF)2)(Ar){Ph2P(Ind)}2] (2a-f) and trans-[Pt(F)(Ar){Ph2P(Ind)}2]

(3a-f) (Ar =Ph (a), 4-FC6H4(b), 4-ClC6H4(c), 4-CH3C6H4) (d), 4-

CF3C6H4) (e), 4-(CH3)3CC6H4) (f)): Solutions of cis-[Pt(CH3)(Ar){R2P-

(Ind)}2] (1a–f) (0.15 mmol) in CD2Cl2or CH2Cl2(2 mL) were added

into PFA-tubes containing PVPHF (150 mg; 38–42 wt% HF). Immedi-

ate gas evolution was overserved, and the mixtures were stirred for

further 5 minutes. The respective solutions were then filtered from

the polymer into PFA-Inliners and analysed by NMR-spectroscopy

revealing the formation of 2a–f. Afterwards, the reaction solutions

of 2a–fwere added into a Schlenk flask loaded with anhydrous CsF

(100 mg) and the mixtures were vigorously stirred for 5 minutes.

After filtration of the solvent were removed in vacuo to give pale-

yellow solids, which were dissolved in CD2Cl2(0.7 mL) and analysed

by NMR spectroscopy revealing the formation of 3a–f. Colourless

crystals of 3a·CH2Cl2,3c ·0.5 CH2Cl2and 3d were obtained by slow

evaporation of the solvent from a dichloromethane solution at

room temperature and were isolated by filtration. 3 a·CH2Cl2was

dried under an argon stream yielding 3a·CH2Cl2(84 mg, 53%) as

colourless crystals. 3c·0.5 CH2Cl2and 3d were dried in vacuo to

give 3c (94 mg, 68%) and 3d (67 mg, 48%) as a colourless solid.

Chemistry—A European Journal

Research Article

doi.org/10.1002/chem.202202768

Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 113/116] 1

Selected analytical data:

trans-[Pt(F·(HF)2)(4-tBuC6H4){Ph2P(Ind)}2] (2a):1H NMR (300.1 MHz,

CD2Cl2, 243 K) δ=11.79 ppm (d, 1J(H,F)=38.1 Hz). 19F NMR

(282.4 MHz, CD2Cl2, 243 K): δ=171.8 (br s, HF), 267.7 ppm (br s

+sat, j1J(F,Pt)j=639 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2,

243 K): δ=7.1 ppm (d+sat, 2J(P,F)=13.4 Hz, 1J(P,Pt)=3164 Hz).

trans-[Pt(F·(HF)2)(4-CH3C6H4){Ph2P(Ind)}2] (2b):1H NMR (300.1 MHz,

CD2Cl2, 243 K) δ=11.84 ppm (d, 1J(H,F)=39.8 Hz). 19F NMR

(282.4 MHz, CD2Cl2, 243 K): δ=171.5 (br s, HF), 269.8 ppm (br s

+sat, j1J(F,Pt)j=626 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2,

243 K): δ=6.2 ppm (d+sat, 2J(P,F)=13.8 Hz, 1J(P,Pt)=3156 Hz).

trans-[Pt(F·(HF)2)(Ph){Ph2P(Ind)}2] (2c):1H NMR (300.1 MHz, CD2Cl2,

243 K) δ=11.87 ppm (d, 1J(H,F)=39.9 Hz). 19F NMR (282.4 MHz,

CD2Cl2, 243 K): δ=177.8 (br s, HF), 270.0 ppm (br s+sat, j

1J(F,Pt)j=620 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2, 243 K): δ=

6.7 ppm (d+sat, 2J(P,F)=14.2 Hz, 1J(P,Pt)=3149 Hz).

trans-[Pt(F·(HF)2)(4-FC6H4){Ph2P(Ind)}2] (2d):1H NMR (300.1 MHz,

CD2Cl2, 243 K) δ=12.01 ppm (d, 1J(H,F)=41.4 Hz). 19F NMR

(282.4 MHz, CD2Cl2, 243 K): δ=126.0 (m, ArF), 171.4 (br s, HF),

274.3 ppm (br s+sat, j1J(F,Pt)j=583 Hz, PtF). 31P{1H} NMR

(121.5 MHz, CD2Cl2, 243 K): δ=6.0 ppm (d+sat, 2J(P,F)=13.3 Hz,

1J(P,Pt)=3099 Hz).

trans-[Pt(F·(HF)2)(4-ClC6H4){Ph2P(Ind)}2] (2e):1H NMR (300.1 MHz,

CD2Cl2, 243 K) δ=12.05 ppm (d, 1J(H,F)=42.0 Hz). 19F NMR

(282.4 MHz, CD2Cl2, 243 K): δ=173.5 (br s, HF), 275.1 ppm (br s

+sat, j1J(F,Pt)j=570 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2,

243 K): δ=5.6 ppm (d+sat, 2J(P,F)=13.4 Hz, 1J(P,Pt)=3091 Hz).

trans-[Pt(F·(HF)2)(4-CF3C6H4){Ph2P(Ind)}2] (2f):1H NMR (300.1 MHz,

CD2Cl2, 243 K) δ=11.92 ppm (d, 1J(H,F)=40.0 Hz). 19F NMR

(282.4 MHz, CD2Cl2, 243 K): δ=62.4 (s, CF3), 173.1 (br s, HF),

275.9 ppm (br s+sat, j1J(F,Pt)j=569 Hz, PtF). 31P{1H} NMR

(121.5 MHz, CD2Cl2, 243 K): δ=6.3 ppm (d+sat, 2J(P,F)=13.7 Hz,

1J(P,Pt)=3080 Hz).

trans-[Pt(F)(4-tBuC6H4){Ph2P(Ind)}2] (3a):1H NMR (300.1 MHz,

CD2Cl2)δ=12.93 ppm (d, 1J(H,F)=50.0 Hz). 1H,15N HMBC

(300.2 MHz/30.4 MHz, CD2Cl2): δ=12.9/238 ppm (dd/dvt, 1J(H,F)=

50 Hz, 1J(NH)=97 Hz/2J(N,F)=34 Hz, N=8 Hz). 19F NMR (282.4 MHz,

CD2Cl2): δ=273.6 ppm (tt+sat, 1J(F,H)=50 Hz, 2J(F,P)=13 Hz, j

1J(F,Pt)j=567 Hz). 31P{1H} NMR (121.5 MHz, CD2Cl2): δ=5.8 ppm (d

+sat, 2J(P,F)=13.1 Hz, 1J(P,Pt)=3176 Hz). Anal. Calcd for

C52H49FN2P2Pt·CH2Cl2: N, 2.64; C, 59.89; H, 4.84. Found: N, 2.91; C,

59.95; H, 4.84.

trans-[Pt(F)(4-CH3C6H4){Ph2P(Ind)}2] (3b):1H NMR (300.1 MHz,

CD2Cl2)δ=12.91 ppm (d, 1J(H,F)=50.1 Hz). 1H,15N HMBC NMR

(300.2 MHz/30.4 MHz, CD2Cl2): δ=12.9/238 ppm (dd/dvt, 1J(H,F)=

50 Hz, 1J(NH)=97 Hz/2J(N,F)=34 Hz, N=8 Hz). 19F NMR (282.4 MHz,

CD2Cl2): δ=274.0 ppm (tt+sat, 1J(F,H)=50 Hz, 2J(F,P)=13 Hz, j

1J(F,Pt)j=564 Hz). 31P{1H} NMR (121.5 MHz, CD2Cl2): δ=5.1 ppm (d

+sat, 2J(P,F)=13.0 Hz, 1J(P,Pt)=3172 Hz).

trans-[Pt(F)(Ph){Ph2P(Ind)}2] (3c):1H NMR (300.1 MHz, CD2Cl2)δ=

12.88 ppm (d, 1J(H,F)=49.6 Hz). 1H,15N HMBC NMR (300.2 MHz/

30.4 MHz, CD2Cl2): δ=12.8/238 ppm (dd/dvt, 1J(H,F)=50 Hz, 1J-

(NH)=97 Hz/2J(N,F)=33 Hz, N=9 Hz). 19F NMR (282.4 MHz, CD2Cl2):

δ=275.2 ppm (tt+sat, 1J(F,H)=50 Hz, 2J(F,P)=14 Hz, j1J(F,Pt)j=

559 Hz). 31P{1H} NMR (121.5 MHz, CD2Cl2): δ=5.5 ppm (d+sat,

2J(P,F)=13.7 Hz, 1J(P,Pt)=3162 Hz). Anal. Calcd for C48H41FN2P2Pt: N,

3.04; C, 62.54; H, 4.48. Found: N, 3.07; C, 62.58; H, 4.50.

trans-[Pt(F)(4-FC6H4){Ph2P(Ind)}2] (3d):1H NMR (300.1 MHz, CD2Cl2)

δ=12.80 ppm (d, 1J(H,F)=48.9 Hz). 1H,15N HMBC NMR (300.2 MHz/

30.4 MHz, CD2Cl2): δ=12.8/239 ppm (dd/dvt, 1J(H,F)=49 Hz, 1J-

(NH)=97 Hz/2J(N,F)=33 Hz, N=8 Hz). 19F NMR (282.4 MHz, CD2Cl2):

δ=126.0 (m, ArF) 278.3 ppm (tt+sat, 1J(F,H)=49 Hz, 2J(F,P)=

14 Hz, j1J(F,Pt)j=521 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2):

δ=5.1 ppm (dd+sat, 2J(P,F)=13.6 Hz, J(P,F)=2.0 Hz, 1J(P,Pt)=

3112 Hz). Anal. Calcd for C48H40F2N2P2Pt: N, 2.98; C, 61.34; H, 4.29.

Found: N, 3.09; C, 61.47; H, 4.30.

trans-[Pt(F)(4-ClC6H4){Ph2P(Ind)}2] (3e):1H NMR (300.1 MHz, CD2Cl2)

δ=12.76 ppm (d, 1J(H,F)=48.6 Hz). 1H,15N HMBC NMR (300.2 MHz/

30.4 MHz, CD2Cl2): δ=12.8/239 ppm (dd/dvt, 1J(H,F)=49 Hz, 1J-

(NH)=97 Hz/2J(N,F)=32 Hz, N=8 Hz). 19F NMR (282.4 MHz, CD2Cl2):

δ=278.7 ppm (tt+sat, 1J(F,H)=48 Hz, 2J(F,P)=14 Hz, j1J(F,Pt)j=

519 Hz, PtF). 31P{1H} NMR (121.5 MHz, CD2Cl2): δ=4.9 ppm (d+sat,

2J(P,F)=13.7 Hz, 1J(P,Pt)=3103 Hz).

trans-[Pt(F)(4-CF3C6H4){Ph2P(Ind)}2] (3f):1H NMR (300.1 MHz,

CD2Cl2)=12.71 ppm (d, 1J(H,F)=47.9 Hz). 1H,15N HMBC NMR

(300.2 MHz/30.4 MHz, CD2Cl2): δ=12.7/239 ppm (dd/dvt, 1J(H,F)=

48 Hz, 1J(NH)=97 Hz/2J(N,F)=31 Hz, N=8 Hz). 19F NMR (282.4 MHz,

CD2Cl2): δ=62.6, (s, CF3), 280.0 ppm (tt+sat, 1J(F,H)=48 Hz,

2J(F,P)=14 Hz, j1J(F,Pt)j=515 Hz, PtF). 31P{1H} NMR (121.5 MHz,

CD2Cl2): δ=5.5 ppm (d+sat, 2J(P,F)=13.5 Hz, 1J(P,Pt)=3090 Hz).

Synthesis of trans-[Pt(Cl)(Ph){Ph2P(Ind)}2] (4): A solution of diphen-

yl-2-(3-methylindolyl)phosphine (0.15 g, 0.48 mmol) in CH2Cl2

(5 mL) was added to a stirring solution of [Pt(Cl)(Ph)(COD)] (0.10 g,

0.24 mmol) in DCM (5 mL). The resulting mixture was stirred for two

hours. The solvent was removed in vacuo to yield the crude product

as a colorless powder. This solid was recrystallised from a solution

of CH2Cl2/n-hexane (20 mL/60 mL) and the product was left to

precipitate overnight. The solution was then filtered off and a

colourless solid was obtained, which was washed with pentane (3×

5 mL) and then dried in vacuo to yield 4as a colourless solid. Yield

0.14 g (62%). IR (ATR, diamond): ~

v=3297 cm1(strong, sharp, NH)

1H NMR (500.1 MHz, CD2Cl2): δ=10.11 (s, 2H, NH), 7.57 (dd, 3J(H,H)=

8.0 Hz, J(H,P)=0.6 Hz, 2H, ArH), 7.45-7.38 (m, 9H, ArH), 7.38-7.33 (m,

5H, ArH), 7.2 9–7.22 (m, 10H, ArH), 7.14-7.09 (m, 2H, ArH), 6.80 (m+

sat., 3J(H,H)=8.0 Hz, 4J(H,P)=1.2 Hz, J(Pt,H)=57 Hz, 2H, ArH, ortho),

6.27 (t, 3J(H,H)=7.3 Hz,1H, ArH, para), 6.15 (t, 3J(H,H)=7.6 Hz, 2H,

ArH, meta), 1.78 (br s, 6H, ArCH3). 31P{1H} NMR (202.5 MHz, CD2Cl2):

δ=8.25 (br s+sat., 1J(Pt,P)=3066 Hz). Anal. Calcd for

C48H41ClN2P2Pt: N, 2.99; C, 61.44; H, 4.40. Found: N, 2.81, C, 61.75, H,

4.34.

Computational Details: All structure optimizations have been

performed with the Turbomole program, version 7.5.1,[43] using the

PBE[44] functional in conjunction with def2-TZVP[45] basis sets for all

atoms. In all calculations the multipole-accelerated resolution-of-

identity approximation (MARIJ)[46] as well as D3[47] empirical

dispersion corrections with Becke-Johnson damping (BJ)[48] was

employed. In addition to gas phase calculations, all structures were

subsequently optimized using the COSMO[49] continuum solvent

model, employing a relative permittivity ɛ=8.9 for dichloro-

methane (DCM, CH2Cl2) as solvent. Based on the optimized

structures, NMR nuclear spin-spin coupling constants were calcu-

lated using the AMS program package, release version 2022.1.[50]

These calculations were performed at the two-component (2c)

quasi-relativistic ZORA[51] all-electron DFT level, employing the

BHLYP[52] functional in conjunction with a locally dense basis set

scheme with all-electron QZ4P-J[53] basis set for the coupling atoms

and otherwise all-electron TZ2P-J[53] basis sets for the remaining

atoms, and a Becke grid of quality 4.[54] Further electronic structure

analyses at BHLYP/def2-TZVP level used the NBO 7.0.7[55] program

linked to the Gaussian 16 program, revision A.03.[56] In this way,

atomic charges from natural population analyses (NPA),[57] atomic

hybridizations from natural localized molecular orbital (NLMO)[57]

analyses, and Wiberg bond indices (WBI)[58] were obtained.

Chemistry—A European Journal

Research Article

doi.org/10.1002/chem.202202768

Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 114/116] 1

Acknowledgements

We gratefully acknowledge financial support from the CRC 1349

funded by the Deutsche Forschungsgemeinschaft (DFG, Ger-

man Research Foundation; Gefördert durch die Deutsche

Forschungsgemeinschaft - Projektnummer 387284271 - SFB

1349). We would like to thank L. Richter and R. Jaeger for

measurements of the low temperature and 1H,15N HMBC NMR

spectra and S. Rachor for scientific discussions. Open Access

funding enabled and organized by Projekt DEAL.

Conflict of Interest

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in

the supplementary material of this article.

Keywords: fluorido complexes ·hydrogen bonding ·

indolylphosphine ·platinum ·polyfluorido complexes

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Manuscript received: September 5, 2022

Accepted manuscript online: November 3, 2022

Version of record online: December 12, 2022

Chemistry—A European Journal

Research Article

doi.org/10.1002/chem.202202768

Wiley VCH Mittwoch, 25.01.2023

2307 / 279198 [S. 116/116] 1