Dal on
T ansac ions
An in e na ional jou nal o ino ganic chemis y
sc.li/dal on
ISSN 1477-9226
Volume 53
Numbe 23
21 June 2024
Pages 9599-10022
PAPER
José M. Vila e al.
Reac i i y o Schi base-[C,N,S] pince palladacycles:
hyd olysis ende s singula inuclea , e anuclea , and
he e open anuclea Pd
3 W
2 coo dina ed complexes
Dal on
T ansac ions
PAPER
Ci e his: Dal on T ans., 2024, 53,
9680
Recei ed 13 h Ma ch 2024,
Accep ed 12 h Ap il 2024
DOI: 10.1039/d4d 00756e
sc.li/dal on
Reac i i y o Schiffbase-[C,N,S] pince
palladacycles: hyd olysis ende s singula
inuclea , e anuclea , and he e open anuclea
Pd
3
W
2
coo dina ed complexes†
F ancisco Reigosa, ‡Paula M. Polo,‡M. Te esa Pe ei a and José M. Vila *
T ea men o he Schiffbase ligands a– wi h Li
2
[PdCl
4
]/NaAcO in me hanol unde eflux ga e he single
nuclea palladacycles 1a–1 , wi h he me al a om bonded o a e den a e monoanionic [C,N,S] iminic
ligand and o a chlo ide ligand ha comple es he palladium coo dina ion sphe e. Reac ion o 1a–1c wi h
sil e pe chlo a e/ iphenylphosphine in ace one a oom empe a u e yielded he single nuclea com-
plexes 2a–2c as he pe chlo a e sal s, a e subs i u ion o he chlo ide ligand by a iphenylphosphine.
Howe e , eac ion o a–cwi h Na
2
[PdCl
4
]/NaAcO in me hanol a oom empe a u e also ga e com-
pounds 1a–1c albei con amina ed wi h small amoun s o he co esponding ee aldehyde (mix u e A).
Reac ion o mix u e A wi h sil e pe chlo a e/ iphenylphosphine in ace one a oom empe a u e ga e
analogously 2a–2c wi h some o he co esponding ee aldehyde (mix u e B). A emp s o pu i y mix u es
A and B ia ec ys alliza ion p oduced single c ys als o 5and 6 espec i ely: wo se endipi ously o med
complexes, bea ing hiome hyl aniline and/o ace a e ligands, and oid o aldehyde o iminic esidue; he
s uc u es con ain eigh - and six-membe ed ings o al e na ing palladium and ni ogen a oms, espec -
i ely. To cla i y his si ua ion he aniline i sel was eac ed wi h palladium(II) ace a e o wi h Na
2
[PdCl
4
]; in
he la e case a e ec ys alliza ion a unique beha io is e ealed, gi ing ise o a e anuclea complex
con aining a Pd
4
N
4
ing wi h h ee diffe ing coo dina ion en i onmen s on he palladium a oms.
T ea men o 1d wi h Ph
2
PCH
2
PPh
2
(dppm)/AgClO
4
o wi h Ph
2
PCH
2
(PPh
2
)W(CO)
5
/AgClO
4
ga e 3d, wi h
a mono-coo dina ed dppm ligand, and 4d, espec i ely; complex 3d could no be con e ed in o 4d by
eac ion wi h W(CO)
5
(THF). Rec ys alliza ion o 4d ga e a s ill u he no iceable species, complex 8:a
pen anuclea ans-configu ed he e ome allic mixed alen Pd(II)/W(0) linea complex wi h he palladium
a oms suppo ed by wo ace a e and wo hiome hyl aniline b idging ligands. The complexes we e ully
cha ac e ized by mic oanalysis, IR,
1
H, and
31
P NMR spec oscopies, as app op ia e. The X- ay single-
c ys al analyses o compounds 1b,5,6,7and 8a e desc ibed.
In oduc ion
The chemis y o palladacycles,
1,2
i s epo ed by Cope and
Siekman,
3
cons i u es a lou ishing pa o o ganome allics
ha has a ac ed much esea ch in e es in pas yea s a ibu-
able o a g ea ex en o hei e sa ile s uc u al and eac i i y
ea u es, mainly de i ed om he ac ha hei p ope ies can
be easily uned, o example by modi ica ion o he cyclome al-
la ed ligand o he ancilla y ligands a he me al. They a e also
well known o hei b oad applica ions
4
in nume ous ields
such as in o ganic syn hesis,
5,6
pho ochemis y,
7,8
op ical
esolu ion p ocesses,
9
and ca alysis, which a e he pionee ing
wo k by He mann e al.,
10,11
con inues o be esea ched,
12–21
as po en ial biologically ac i e ma e ials,
22–31
and liquid
c ys als.
32–34
In he pas we ha e shown ha hiosemica bazones yield
palladacycles wi h he ligand in a e den a e [C,N,S] ashion
35
wi h o ma ion o e anuclea compounds possessing wo
dis inc palladium–sul u bonds, i.e.,Pd–S
chela ing
and
Pd–S
b idging
, wi h he ligand in a pince mode; Kawamo o e al.
36
ha e epo ed simila s uc u es o Schiffbase [C,N,S] Pd(II)and
P (II) complexes. This esul s in h ee s ong bonds a he me al,
namely he Pd–C, Pd–NandPd–S
chela ing
bonds pe aining o wo
used i e-membe ed ings, ha main ain he me al igh ly
bonded so ha only one o he ou coo dina ion si es in he
†CCDC 2333528 (1b), 2333529 (5), 2333530 (7), 2333531 (6) and 2333532 (8). Fo
c ys allog aphic da a in CIF o o he elec onic o ma see DOI: h ps://doi.o g/
10.1039/d4d 00756e
‡Bo h au ho s con ibu ed equally.
Depa amen o de Química Ino gánica, Uni e sidad de San iago de Compos ela,
E-15782 San iago de Compos ela, Spain. E-mail: josem[email p o ec ed]
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squa e-plana palladium en i onmen is capable o u he eac-
ion. Ea lie esul s by his labo a o y also pu o wa d ha he
said complexes eac wi h small bi e s ong chela ing dipho-
sphines o gi e species wi h an uncoo dina ed phospho us dono
a om,
37
hus pe o ming as me alloligands, which we e able o
coo dina e o a second me al a om, p o iding homo- and he e o-
bime allics. We hen sough ou o look o analogous sys ems
ha would e ain he excellen pince p ope ies o he e den a e
[C,N,S] ligands and o his pu pose Schiffbases de i ed om
2- hiome hylaniline we e chosen; his changes he hiosemica ba-
zone sequence –C(Me) N–N(H)–C(NHR)–S o he co es-
ponding Schiffbase one –C(H) N–C C–SMe. We easoned
ha hese ela ed sys ems bea ing analogous backbones o
ni ogen and sul u dono s would beha e likewise and e en in
he absence o he hiola e sul u he non- hiola e hiome hyl
g oup would bind well in ag eemen wi h Pea son’s concep .
38
The p epa a ion o [C,N,S] me allacycles can be achie ed by
qui e nume ous ou es such as eac ions wi h li hium de i a-
i es,
39
oxida i e addi ion and pho ooxida ion,
40
and di ec
o home alla ion o which Pd(DMSO)
2
Cl
2
,
41
Pd(OAc)
2
,
Li
2
[PdCl
4
]o Na
2
[PdCl
4
] a e amongs he mo e common
eagen s. The li hium sal has p o en o be a qui e use ul pal-
ladium sou ce o he syn hesis o palladacycles, and was used
in he p esen p epa a ions, albei equi es p io syn hesis o
he sal using mois u e-sensi i e eagen s; he e o e, he com-
me cially a ailable sodium sal was also used o compa e
esul s and o educe he syn he ic s eps. Thus, he la e wo
we e chosen and al hough he ini ial s eps seemed o ag ee
wi h he expec a ions he ensuing iminic me alloligands and
he co esponding bime allics simila o hose men ioned
abo e, could no be p epa ed om he sodium sal , d i ing
he p ocess o a diffe en ou e: we en a i ely a ibu e his o
pa ial hyd olysis o he iminic ligand. The spon aneous decay
o he p oduc s yielded unp eceden ed ea angemen s
p oducing i- and e anuclea homome allic complexes,
wi h he me hyl hioaniline p ecu so simul aneously ac ing
as a chela ing and b idging ligand, leading o new insigh s
in o hei chemis y. This led us o s udy he eac i i y o
he 2- hiome hylaniline i sel o es ou hypo hesis.
Fu he mo e, he bime allic palladium/ ungs en also decayed
on ec ys alliza ion o yield a pen anuclea he e ome allic
complex. A mo e ecen example ela ed o spon aneous pal-
ladacycle dis up ion has been epo ed by us ela ed o he
Schiffbase palladacycles: an inno a e s uc u al ea ange-
men om single-nuclea o double-nuclea pseudo-pen a-
coo dina ed complexes, ha we da e say is e en mo e su -
p ising since i could be e med as a special case o sel -
cyclopallada ion.
42
We en a i ely coin hese p ocesses as
ypical cases o se endipi y in palladacycle chemis y, which
on he o he hand pu o wa d no el and exci ing eac i i y
pa e ns ye o be accoun ed o , de eloping new subs ances
ha may be o use in any o he ields o applica ion o
hese compounds.
In his wo k we epo palladacycles bea ing iden a e
[C,N,S] Schiffbase ligands and diffe ing palladium sal s,
oge he wi h he co esponding eac ions wi h mono- and
diphosphines, leading o he disco e y o new mul inuclea
complexes.
Expe imen al sec ion
Gene al p ocedu es
Sol en s we e pu i ied by s anda d me hods. Chemicals
(li hium chlo ide, palladium(II) chlo ide), he phosphines PPh
3
and Ph
2
PCH
2
PPh
2
(dppm), aldehydes and 2- hiome hyl aniline
we e used as supplied om comme cial sou ces. Li hium e a-
chlo opallada e was made in si u by ea ing palladium(II)
chlo ide wi h li hium chlo ide in me hanol. Ph
2
PCH
2
P(Ph
2
)W
(CO)
5
was p epa ed by li e a u e syn hesis. Mic oanalyses we e
ca ied ou a he Se icio de Análisis Elemen al a he
Uni e si y o San iago using a FISONS elemen al analyze ,
Model 1108. IR spec a we e eco ded as KB pelle s o poly-
hene discs on BRUKER Model IFS-66 and IR-FT Ma son
Model Cygnus-100 spec opho ome e s, and on a JASCO FT/
IR-4600 spec ome e equipped wi h an ATR, model ATR-PRO
ONE. NMR spec a we e ob ained as CDCl
3
, DMSO-d
6
o
Me
2
CO-d
6
solu ions as app op ia e and e e enced o SiMe
4
(
1
H) o 85% H
3
PO
4
(
31
P–{
1
H}) and we e eco ded on BRUKER
DPX 250 and Va ian Ino a 400 spec ome e s. All chemical
shi s, in ppm, we e epo ed down ield om he s anda ds.
Syn heses
P epa a ion o he ligands
The co esponding aldehyde and 2- hiome hyl aniline we e
added oge he in chlo o o m (ca.30cm
3
) in a ound-bo -
omed lask o gi e a pale-yellow solu ion which was e luxed
in a modi ied Dean–S a k appa a us unde d y ni ogen o
24 h, a e which he esul ing yellow o da k-yellow solu ion
was cooled o oom empe a u e and he sol en emo ed
unde educed p essu e.
3,4-(OMe)
2
C
6
H
3
C(H) N[2-(SMe)C
6
H
4
]a.Yellow solid. Yield:
87%.
1
H NMR (400 MHz, DMSO-d
6
)δ8.40 (s, 1H, HC N), 7.66
(s, 1H, H2), 7.47 (dd,
3
J= 8.3 Hz,
4
J= 1.9 Hz, 1H, H6), 7.24 ( d,
3
J= 7.3 Hz,
4
J= 1.7 Hz, 1H, H10), 7.19 (d,
3
J= 7.3 Hz, 1H. H11),
7.15 ( d,
3
J= 7.3 Hz,
4
J= 1.7 Hz, 1H, H9), 7.08 (dd,
3
J= 8.3 Hz,
4
J= 2.0 Hz, 1H, H5), 7.04 (dd,
3
J= 7.6 Hz,
4
J= 1.7 Hz, 1H, H8),
3.89 (s, 6H, OMe), 2.42 (s, 3H, SMe). IR cm
−1
ν(C N) 1618.
Anal. ound: C, 67.1; H, 5.9; N, 5.0; S, 10.9%, C
16
H
17
NO
2
S
(287.38 g mol
−1
) equi es C, 66.9; H, 6.0; N, 4.9; S, 11.2%.
3-Me-4-OMeC
6
H
3
C(H) N[2-(SMe)C
6
H
4
]b.Yellow solid.
Yield: 92%.
1
H NMR (400 MHz, DMSO-d
6
)δ8.39 (s, 1H,
HC N), 7.82 (d,
4
J= 2.1 Hz, 1H, H2), 7.77 (dd,
3
J= 8.4 Hz,
4
J=
2.3 Hz, 1H, H6), 7.23 ( d,
3
J= 7.4 Hz,
4
J= 1.7 Hz, 1H, H10),
7.18 (dd,
3
J= 7.7 Hz,
4
J= 1.7 Hz, 1H, H11), 7.15 ( d,
3
J= 7.4 Hz,
4
J= 1.8 Hz, 1H), 7.06 (d,
3
J= 8.4 Hz, 1H, H5), 7.03 (dd,
3
J= 7.5
Hz,
4
J= 1.6 Hz, 1H, H8), 3.93 (s, 3H, OMe), 2.42 (s, 3H, SMe),
2.25 (s, 3H, Me). IR cm
−1
ν(C N) 1625. Anal. ound: C, 70.5;
H, 6.2; N, 5.2; S, 11.9%, C
16
H
17
NOS (271.38 g mol
−1
) equi es
C, 70.8; H, 6.3; N, 5.2; S, 11.8%.
Dal on T ansac ions Pape
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3,4-(OCH
2
CH
2
O)C
6
H
3
C(H) N[2-(SMe)C
6
H
4
]c.O ange oil.
Yield: 88%.
1
H NMR (400 MHz, ace one-d
6
)δ8.38 (s, 1H,
HC N), 7.52 (s, 1H, H2), 7.46 (d,
3
J= 8.7 Hz, 1H, H6), 7.23 (m,
2H, H9/H11), 7.18–7.13 (m, 1H), 7.04 (d,
3
J= 8.2 Hz, 1H, H8),
6.96 (d,
3
J= 8.3 Hz, 1H, H5), 4.34 (d,
3
J= 5.4 Hz, 4H, CH
2
), 2.42
(s, 3H, SMe). IR cm
−1
ν(C N) 1621. Anal. ound: C, 67.1; H,
5.3; N, 4.7; S, 11.5%, C
16
H
15
NO
2
S (285.36 g mol
−1
) equi es C,
67.3; H, 5.3; N, 4.9; S, 11.2%.
4-OMeC
6
H
4
C(H) N[2-(SMe)C
6
H
4
]d.Yellow oil. Yield 85%.
1
H NMR (250 MHz, DMSO-d
6
)δ8.44 (s, 1H, HC N), 7.88 ( d,
N= 8.0 Hz, 2H, H2, H6), 7.10–7.30 (m, 4H, H9, H10, H11,
H12), 7.07 ( d, N= 8.0 Hz, 2H, H3, H5), 3.82 (s, 3H, OMe), 2.37
(s, 3H, SMe). IR cm
−1
ν(C N) 1626. Anal. ound: C, 70.1; H,
6.0; N, 5.7; S, 12.3%, C
15
H
15
NOS (257.35 g mol
−1
) equi es C,
70.0; H, 5.9; N, 5.4; S, 12.5%.
2,4-(OMe)
2
C
6
H
4
C(H) N[2-(SMe)C
6
H
4
]e.Yellow oil. Yield
82%.
1
H NMR (250 MHz, CDCl
3
)δ8.73 (s, 1H, HC N), 8.19 (d,
3
J(H6H5) = 8.7 Hz, 1H, H6), 6.93–7.17 (m, 4H, H9, H10, H11,
H12), 6.56 (dd,
3
J(H5H6) = 8.7 Hz,
4
J(H5H3) = 2.3 Hz, 1H, H5),
6.43 (d,
4
J(H3H5) = 2.3 Hz, 1H, H3), 3.84 (s, 3H, OMe), 3.82 (s,
3H, OMe), 2.42 (s, 3H, SMe). IR cm
−1
ν(C N) 1601. Anal.
ound: C, 67.0; H, 5.9; N, 5.0; S, 11.0%, C
16
H
17
NO
2
S (287.38 g
mol
−1
) equi es C, 66.8; H, 6.0; N, 4.9; S, 11.2%.
2,3,4-(OMe)
3
C
6
H
4
C(H) N[2-(SMe)C
6
H
4
] .Yellow oil. Yield
98%.
1
H NMR (250 MHz, CDCl
3
): δ8.65 (s, 1H, HC N), 7.97
(d,
3
J(H6H5) = 8.8 Hz, 1H, H6), 6.70–7.18 (m, 4H, H9, H10,
H11, H12), 6.96 (d,
3
J(H5H6) = 8.8 Hz, 1H, H5), 3.94 (s, 3H,
OMe), 3.90 (s, 3H, OMe), 3.87 (s, 3H, OMe), 2.43 (s, 3H, SMe).
IR cm
−1
ν(C N) 1623. Anal. ound: C, 64.1; H, 6.0; N, 4.5; S,
10.2%, C
17
H
19
NO
3
S (317.40 g mol
−1
) equi es C, 64.3; H, 6.0;
N, 4.4; S, 10.1%.
P epa a ion o he chlo ide compounds
Rou e a: Palladium chlo ide and li hium chlo ide we e added
oge he in oxygen- ee me hanol in a ca ousel lask unde
a gon. The mix u e was s i ed a oom empe a u e un il a
eddish colo appea ed. Then, he ligand was added and a
colo change was obse ed, ollowed by u bidi y and by he
o ma ion o a solid wi hin he solu ion. The eac ion mix u e
was hea ed o 70 °C o 4 h and one equi alen o sodium
ace a e was added, which p oduced he ins an aneous o -
ma ion o an o ange solid ha was sepa a ed by
cen i uga ion.
Rou e b: In a 100 mL ound bo om lask he ligand was
dissol ed in me hanol wi h s i ing and a oom empe a u e.
Then, sodium e achlo opallada e was added, ollowed by
sodium ace a e, and upon u he s i ing he o ma ion o an
o ange p ecipi a e was obse ed. The solid was sepa a ed by il-
a ion, washed and d ied unde acuum.
Rou e c ( o 1d,1e,1 ): To a s i ed da k- ed solu ion o
li hium e achlo opallada e(II) in me hanol he ligand, d,e, ,
was added and he mix u e was e luxed o 1 h unde d y dini-
ogen. A e cooling o oom empe a u e sodium ace a e was
added o he esul ing solu ion. The solid o med was il e ed
off, washed wi h e hanol and ai -d ied.
[Pd{3,4-(OMe)
2
C
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1a. O ange
solid. Yield: 58%.
1
H NMR (400 MHz, CDCl
3
)δ8.51 (s, 1H,
HC N), 7.60 (d,
3
J= 8.0 Hz, 1H, H11), 7.57 ( ,
3
J= 8.0 Hz, 1H,
H10), 7.46 (s, 1H, H2), 7.45 ( d,
3
J=8.4Hz,
4
J= 1.4 Hz, 1H, H9),
7.40–7.33 (m, 1H), 7.02 (s, 1H, H5), 4.01 (s, 3H, OMe), 3.86 (s, 3H,
OMe), 2.81 (s, 3H, SMe). IR cm
−1
ν(C N) 1579; ν(Pd–Cl) 322.
Anal. ound: C, 45.1; H, 3.8; N, 3.5; S, 7.3%, C
16
H
16
ClNO
2
PdS
(428.24 g mol
−1
) equi es C, 44.9; H, 3.8; N, 3.3; S, 7.5%.
[Pd{3-Me-4-OMeC
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1b. O ange
solid. Yield: 63%.
1
H NMR (400 MHz, CDCl
3
)δ8.47 (s, 1H,
HC N), 7.60 (dd,
3
J= 8.5 Hz,
4
J= 1.2 Hz, 1H), 7.57 (dd,
3
J= 7.8
Hz,
4
J= 1.5 Hz, 1H), 7.44 ( d,
3
J= 8.4 Hz,
4
J= 1.5 Hz, 1H), 7.39
(s, 1H, H2), 7.38–7.29 (m, 2H), 3.96 (s, 3H, OMe), 2.81 (s, 3H,
SMe), 2.14 (s, 3H, Me). IR cm
−1
ν(C N) 1581; ν(Pd–Cl) 329.
Anal. ound: C, 46.7; H, 3.9; N, 3.6; S, 7.9%, C
16
H
16
ClNOPdS
(412.24 g mol
−1
) equi es C, 46.6; H, 3.9; N, 3.4; S, 7.8%.
[Pd{3,4-(OCH
2
CH
2
O)C
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1c.
O ange solid. Yield: 74%.
1
H NMR (400 MHz, ace one-d
6
)δ
9.01 (s, 1H, HC N), 7.99 (d,
3
J= 8.4 Hz, 1H, H11), 7.81 (d,
3
J=
7.8 Hz, 1H, H8), 7.58 ( ,
3
J= 7.4 Hz, 3H, H10), 7.48 ( ,
3
J= 8.0
Hz, 1H, H9), 7.21 (s, 1H, H2), 7.14 (s, 1H, H5), 7.34 (d, J= 4.1
Hz, 2H, CH
2
), 4.27 (s, 2H, CH
2
), 2.82 (d, J= 1.6 Hz, 3H, SMe).
IR cm
−1
ν(C N) 1581; ν(Pd–Cl) 327. Anal. ound: C, 44.8; H,
3.2; N, 3.1; S, 7.2%, C
16
H
14
ClNO
2
PdS (426.22 g mol
−1
) equi es
C, 45.1; H, 3.3; N, 3.3; S, 7.5%.
[Pd{4-OMeC
6
H
3
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1d. Yellow solid.
Yield 83%.
1
H NMR (250 MHz, DMSO-d
6
): δ9.12 (s, 1H, HC N),
7.98 (d,
3
J(H11H12) = 8.4 Hz, 1H, H12), 7.83 (d,
3
J(H9H10) = 7.9
Hz, 1H, H9), 7.55 ( ,
3
J(H10H11) = 8.0 Hz, 1H, H10), 7.53 (d,
3
J(H2H3) = 8.8 Hz, 1H, H2), 7.44 ( , 1H, H11), 7.11 (d,
4
J(H5H3) =
2.7 Hz, 1H, H5), 6.71 (dd, 1H, H3), 3.80 (s, 3H, OCH
3
), 2.75 (s,
3H, SCH
3
). IR 1603 ν(C N), 315 ν(Pd–Cl
ans-N
)cm
−1
. Anal. ound:
C, 45.0; H, 3.4; N, 3.4; S, 8.0%, C
15
H
14
ClNOPdS (398.22 g mol
−1
)
equi es C, 45.2; H, 3.5; N, 3.5; S, 8.1%.
[Pd{2,4-(OMe)
2
C
6
H
3
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1e. O ange
solid. Yield 77%.
1
H NMR (250 MHz, CDCl
3
)δ8.77 (s, 1H,
HC N), 7.61 (d,
3
J(H11H12) = 8.2 Hz, 1H, H12), 7.51 (d,
3
J(H9H10) = 7.8 Hz, 1H, H9), 7.39 ( , 1H, H10), 7.27 ( , 1H,
H11), 7.03 (d,
4
J(H5H3) = 2.1 Hz, 1H, H5), 6.06 (d,
4
J(H3H5) =
2.1 Hz, 1H, H3), 3.89 (s, 3H, OMe), 3.80 (s, 3H, OMe), 2.77 (s,
3H, SMe). IR 1585 ν(C N), 332 ν(Pd–Cl
ans-N
)cm
−1
. Anal.
ound: C, 45.1; H, 3.8; N, 3.2; S, 7.4%, C
16
H
16
ClNO
2
PdS
(428.24 g mol
−1
) equi es C, 44.9; H, 3.8; N, 3.3; S, 7.5%.
[Pd{2,3,4-(OMe)
3
C
6
H
3
C(H) N[2-(SMe)C
6
H
4
]}(Cl)] 1 . Yellow
solid. Yield 82%.
1
H NMR (250 MHz, CDCl
3
)δ8.73 (s, 1H,
HC N), 7.64 (d,
3
J(H12H11) = 8.3 Hz, 1H, H12), 7.54 (d,
3
J(H9H10) = 7.7 Hz, 1H, H9), 7.42 ( ,
3
J(H10H11) = 7.2 Hz, 1H,
H10), 7.15 (s, 1H, H5); 7.30 ( , 1H, H11), 4.02 (s, 3H, OMe),
3.95 (s, 3H, OMe), 3.77 (s, 3H, OMe), 2.76 (s, 3H, SMe). IR 1606
ν(C N), 333 ν(Pd–Cl
ans-N
)cm
−1
. Anal. ound: C, 44.5; H, 3.9;
N, 3.2; S, 7.1%, C
17
H
18
ClNO
3
PdS (458.27 g mol
−1
) equi es C,
44.6; H, 4.0; N, 3.1; S, 7.0%.
P epa a ion o he iphenylphosphine palladacycles
The app op ia e palladacycle and sil e pe chlo a e we e added
in ace one (15 mL) in a ca ousel ube o gi e a ligh o ange
Pape Dal on T ansac ions
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solu ion, which was s i ed o 10 min. Then, he solu ion
becomes da k o ange and he esul ing whi e solid (AgCl) was
emo ed by cen i uga ion p io o addi ion o iphenyl-
phosphine. Remo al o he sol en unde educed p essu e
ga e he expec ed complex as an o ange solid, which was il-
e ed offand d ied.
[Pd{3,4-(OMe)
2
C
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(PPh
3
)][ClO
4
] 2a.
O ange solid. Yield: 78%.
1
H NMR (400 MHz, ace one-d
6
)δ
9.29 (d,
4
J
P–H
= 9.3 Hz, 1H, HC N), 8.05 (d,
3
J= 8.4 Hz, 1H,
H11), 7.89–7.81 (m, 7H), 7.74–7.51 (m, 9H), 7.43 (s, 1H, H2),
6.83 ( ,
3
J= 7.8 Hz, 1H, H9), 6.61 ( ,
3
J= 7.8 Hz, 1H, H10), 6.05
(d,
4
J
P–H
= 5.3 Hz, 1H, H5), 3.76 (s, 3H, OMe), 2.93 (s, 3H,
OMe), 2.12 (s, 3H, SMe).
31
P-NMR (400 MHz, ace one-d
6
)δ
38.89. IR ν(C N) 1582; ν(ClO
4
) 1094 cm
−1
. Anal. ound: C,
53.8; H, 3.9; N, 1.8; S, 4.1%, C
34
H
31
ClNO
6
PPdS (754.53 g
mol
−1
) equi es C, 54.1; H, 4.1; N, 1.9; S, 4.3%.
[Pd{3-Me-4-OMeC
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(PPh
3
)][ClO
4
]
2b. O ange solid. Yield: 80%.
1
H NMR (400 MHz, ace one-d
6
)δ
9.25 (d,
4
J
P–H
= 9.1 Hz, 1H, HC N), 8.06 (d,
3
J= 8.6 Hz, 1H,
H11), 7.85 (dd, J= 12.4, 8.0 Hz, 6H), 7.74–7.56 (m, 9H), 7.51 (d,
J= 6.8 Hz, 11H), 7.43 (s, 1H, H2), 6.84 ( , J= 7.9 Hz, 1H, H9),
6.62 ( , J= 7.9 Hz, 1H, H10), 6.05 (d,
4
J
P–H
= 4.3 Hz, 1H, H5),
2.95 (s, 3H, OMe), 2.26 (s, 3H, Me), 2.12 (s, 3H, SMe).
31
P-NMR
(400 MHz, ace one-d
6
)δ37.49. IR cm
−1
ν(C N) 1582; ν(ClO
4
)
1091. Anal. ound: C, 55.1; H, 4.1; N, 1.9; S, 4.4%,
C
34
H
31
ClNO
5
PPdS (738.53 g mol
−1
) equi es C, 55.3; H, 4.2; N,
1.9; S, 4.3%.
[Pd{3,4-(OCH
2
CH
2
O)C
6
H
2
C(H) N[2-(SMe)C
6
H
4
]}(PPh
3
)][ClO
4
]
2c. O ange solid. Yield: 85%.
1
H NMR (400 MHz, ace one-d
6
)δ
9.30 (d,
4
J
P–H
= 9.0 Hz, 1H, HC N), 8.10 (d,
3
J= 8.3 Hz, 1H,
H11), 8.06–7.97 (m, 6H), 7.78–7.49 (m, 9H), 7.46 ( ,
3
J= 7.6 Hz,
1H, H10), 7.36 (m, 1H, H9), 7.09 (s, 1H, H2), 7.02 (s, 1H, H2),
5.95 (d,
4
J
P–H
= 5.0 Hz, 1H, H5), 4.17–4.10 (m, 4H, OCH
2
CH
2
O),
2.14 (s, 3H, SMe).
31
P-NMR (400 MHz, ace one-d
6
)δ38.54. IR
cm
−1
ν(C N) 1576; ν(ClO
4
) 1094. Anal. ound: C, 54.5; H, 3.9;
N, 2.1; S, 4.1%, C
34
H
29
ClNO
6
PPdS (752.51 g mol
−1
) equi es C,
54.3; H, 3.9; N, 1.9; S, 4.3%.
Reac i i y o 2-me hyl hio aniline
Rou e a: Palladium ace a e was in oduced in o a ca ousel ube
i ed wi h a s i ing ba . 10 mL o oluene a e added, and a
pa ial dissolu ion o palladium sal is obse ed.
Me hyl hioaniline is hen in oduced, and i is obse ed ha
he solu ion becomes o ange. I is allowed o eac wi h s i ing
a 50 °C o 24 h, a e which he o ma ion o a yellow solid is
obse ed wi hin he solu ion ha is sepa a ed by cen i u-
ga ion. The supe na an is b ough o d yness, esul ing in an
o ange solid.
1
H NMR (400 MHz, ace one-d
6
)δ7.27 (d,
3
J= 7.6
Hz, 1H), 7.02 ( ,
3
J= 7.7 Hz, 1H), 6.77 (d,
3
J= 8.1 Hz, 1H), 6.59
( ,
3
J= 7.5 Hz, 1H), 4.91 (d,
3
J= 10.2 Hz, 2H), 2.31 (s, 3H).
Rou e b: In a ca ousel ube i ed wi h a s i ing ba sodium
e achlo opallada e was added in me hanol (10 mL) and a
eddish solu ion was o med; which quickly changes o yellow
upon addi ion o me hyl hioaniline. The eac ion mix u e was
s i ed o 24 h and a whi e solid o med was sepa a ed by cen-
i uga ion, a e which he esul ing solu ion was educed o
low olume o gi e an o ange solid.
1
H NMR (400 MHz,
DMSO-d
6
)δ7.84 (d,
3
J= 7.7 Hz, 1H), 7.48 ( ,
3
J= 7.5 Hz, 1H),
7.42 ( ,
3
J= 7.5 Hz, 1H), 7.33 (d,
3
J= 7.9 Hz, 1H), 7.18 (d,
3
J=
7.7 Hz, 1H), 6.97 ( ,
3
J= 7.7 Hz, 1H), 6.68 (d,
3
J= 8.0 Hz, 1H),
6.53 ( ,
3
J= 7.5 Hz, 1H), 5.16 (s, 2H, NH), 2.84 (s, 3H, SMe),
2.29 (s, 3H, SMe).
P epa a ion o he diphosphine palladacycles
[Pd{4-OMeC
6
H
3
C(H) N[2-(SMe)C
6
H
4
]}(PPh
2
CH
2
PPh
2
-P)]
(ClO
4
) (3d). Sil e pe chlo a e (10.4 mg, 0.05 mmol) was added
o a suspension o he cyclome alla ed complex 1a (20 mg,
0.05 mmol) in ace one (15 cm
3
). The mix u e was s i ed o
4 h a . . and il e ed o e Celi e o emo e he sil e chlo ide
p ecipi a e. PPh
2
CH
2
PPh
2
(19 mg, 0.05 mmol) was added o
he il a e and he solu ion s i ed o 24 h a . ., he sol en
was emo ed and he esidue was ec ys allized om dichlo o-
me hane/hexane. O ange solid. Yield 78%.
1
H NMR (400 MHz,
CDCl
3
)δ8.88 (d, 1H, HC N,
4
J
P–H
= 8.4 Hz), 7.30–7.80 (m,
20H, PPh
2
); H2, 7.70–7.00 (H10–H12 hidden by he esonance
o a oma ic phosphine sys em), 7.15 (d, 1H, H9), 6.61 (d, 1H,
H3,
3
J(H2H3) = 7.5 Hz), 5.84 (s, 1H, H5), 4.19 ( a, 2H, PCH
2
P,
2
J(HP) = 2.4 Hz), 3.22 (s, 3H, OCH
3
), 2.07 (s, 3H, SCH
3
).
31
P
NMR (400 MHz, CDCl
3
)δ−23.60 (d,
2
J(PP) = 51.5 Hz); 31.30
(d,
2
J(PP) = 51.5 Hz). IR cm
−1
ν(C N) 1598; ν(ClO
4
) 1093. Anal.
ound: C, 56.8; H, 4.3; N, 1.7; S, 4.3%, C
40
H
36
ClNO
5
P
2
Pd
S
(846.60 g mol
−1
) equi es C, 57.0; H, 4.2; N, 1.6; S, 3.8%.
[Pd{2,4-(OMe)
2
C
6
H
3
C(H) N[2-(SMe)C
6
H
4
]}(PPh
2
CH
2
P(Ph
2
)
W(CO)
5
-P)](ClO
4
) (4d). To a suspension o 1e (20 mg,
0.05 mmol) in ace one (15 cm
3
). AgClO
4
was added. The
mix u e was s i ed o 4 h, a e which ime he sil e chlo ide
o med was il e ed off h ough Celi e. PPh
2
CH
2
P(Ph
2
)W(CO)
5
(11 mg, 0.025 mmol) was added o he il a e and he solu ion
s i ed o 4 h; educing o low olume ga e a solid which was
il e ed offand d ied. Yellow solid. Yield 53% (1200.52).
Calc. ound.
1
H NMR (400 MHz, CDCl
3
)δ8.90 (d, 1H, HC N,
4
J
P–H
= 7.6 Hz), 7.70–7.00 (H9–H12 hidden by he esonance o
a oma ic phosphine sys em), 6.42 (d,
2
J(PP) = 72.0 Hz,
1
J(PW)
= 247.9 Hz), 6.02 (d, 1H, H3,
4
J(H3H5) = 3.2 Hz), 5.55 (dd, 1H,
H5,
4
J(H5H3) = 3.2 Hz,
4
J(H5P) = 7.1 Hz), 4.93 ( , 1H, CH
2
,
2
J(HP) = 9.3 Hz,
2
J(HP) = 11.5 Hz), 3.98 (dd, 1H, CH
2
,
2
J(HP) =
6.3 Hz,
2
J(HP) = 11.7 Hz), 3.82 (s, 3H, OCH
3
), 3.40 (s, 3H,
OCH
3
), 1.70 (s, 3H, SCH
3
).
31
P NMR (400 MHz, CDCl
3
)δ26.6
(d,
2
J(PP) = 72.0 Hz); IR cm
−1
ν(C N) 1583; ν(ClO
4
) 1095. Anal.
ound: C, 45.8; H, 3.3; N, 1.7; S, 3.2%, C
46
H
38
ClNO
11
P
2
PdSW
(1200.52 g mol
−1
) equi es C, 46.0; H, 3.2; N, 1.2; S, 2.7%.
Resul s and discussion
Fo he con enience o he eade he compounds and eac-
ions a e shown in Schemes 1–3. The compounds desc ibed in
his pape we e cha ac e ized by elemen al analysis (C, H, N,
S), and by IR spec oscopy, and by
1
H,
31
P–{
1
H} spec oscopy
and, in pa , c ys al s uc u e analysis (see Expe imen al,
Table 1 and Fig. 1–5).
Dal on T ansac ions Pape
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The Schiffbase ligands a– we e p epa ed by eac ion o
2- hiome hylaniline wi h he co esponding aldehyde o gi e
pu e ai -s able solids which we e ully cha ac e ized.
Dis inc i e o he spec um o dwe e he wo i ual double s
s emming om he a oma ic AA′XX′spin sys em wi h N=
8.0 ppm. T ea men o he ligands wi h Li
2
[PdCl
4
]/NaAcO in
me hanol ga e he palladacycles 1a–1c (Scheme 1) and 1d–1
(Scheme 3) ha we e isola ed as ai -s able solids wi h he
ligand in a iden a e [C,N,S] coo dina ion mode; p epa a i e
de ails and cha ac e is ic mic oanaly ical and spec oscopic
da a a e gi en in he Expe imen al sec ion. No ewo hy o
men ion a e he shi o he ν(C N) s e ch o lowe wa enum-
be s by ca.40cm
−1
in he IR spec a, and absence o he C(6)–
H esonance in he NMR spec a;
43
also, he SMe esonance
was down ield shi ed in he
1
H NMR spec a, ca. 0.4 ppm, in
ag eemen wi h Pd–S coo dina ion, and he me alla ed ligand
o 1d showed he absence o he AA′XX′sys em consequen on
Pd–C bond o ma ion.
C ys al s uc u e o 1b
Sui able c ys als we e g own by slow e apo a ion o a chlo o-
o m solu ion. The c ys al s uc u e o 1b (Fig. 1 and Table 1)
consis s o molecules wi h he palladium(II) a om bonded in a
sligh ly dis o ed squa e-plana en i onmen o ou diffe en
dono a oms, he a yl C(6) ca bon, he iminic N(1) ni ogen,
and he S(1) sul u a oms, o he iden a e iminic and o he
chlo ine a om Cl(1). The sul u a om in SMe becomes a chi al
cen e upon me ala ion, and in he s uc u e he e is a acemic
mix u e o bo h enan iome s. The angles be ween adjacen
a oms in he palladium coo dina ion sphe e a e ca. 90° wi h
he mos no iceable dis o ion in he N(1)2Pd(1)2C(6) angle o
81.7(2)°, a consequence o chela ion; he sum o angles a ound
he palladium a om is 360.03°. All bond leng hs a e wi hin he
expec ed ange, wi h allowance o Pd(1)2C(1) leng h, o 2.044
(4) Å, sho e han he expec ed alue o 2.081 Å
44
sugges ing
some deg ee o mul iple bond cha ac e in he Pd2C(a yl)
linkage.
45
Reac ion o 1a–1c wi h PPh
3
/AgClO
4
ga e complexes 2a–2c,
a e abs ac ion o he chlo ide ion as AgCl, which we e ully
cha ac e ized (see Expe imen al). A emp s o p oduce species
Scheme 1 Reac ion sequence leading o he syn hesis o he compounds.
Scheme 2 Reac i i y o 2- hiome hyl aniline wi h diffe ing palladium
eagen s.
Pape Dal on T ansac ions
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wi h simul aneous linkage o he phosphine and chlo ide
ligands o he me al we e o no a ail; his is in keeping wi h a
a he s ong Pd–S bond. The IR spec a showed absence and
o he ν(Pd–Cl) band; whils he
1
H NMR spec a he H(5) was
up ield shi ed and coupled o he phospho us esonance.
To s udy he sui abili y o o he me alla ing agen s a
sligh ly diffe en syn he ic app oach was es ed wi h ligands a–
c; his allowed disclosu e o a new pe o mance o he ligands
and complexes. Thus, ea men o ligands a–cwi h
Na
2
[PdCl
4
]/NaAcO in me hanol ga e a solu ion con aining he
1a–1c complexes, wi h analogous spec oscopic ea u es as
hose desc ibed abo e, plus he s a ing aldehyde and amine,
o which he
1
H NMR spec a showed he signals o he
HC O, NH
2
and SMe esonances ca. 10, 6.7 and 2.3 ppm,
espec i ely, oge he wi h o he a oma ic esonances (mix u es
ype A). This did no seem o be unusual because in he p e-
ious eac ions using Li
2
[PdCl
4
] as me al sal , p io o addi ion
o he base, aliquo s o he eac ion mix u e we e aken and
some ee aldehyde was obse ed due o pa ial hyd olysis;
howe e , in hose cases a e addi ion o NaAcO and ensuing
wo k up he inal compounds we e ob ained pu e ( ide sup a).
Then, ea men o he said mix u e A wi h PPh
3
/AgClO
4
yielded compounds 2a–2c impu i ied wi h ee aldehyde and
amine (mix u es ype B). To sepa a e he palladacycles and
con i m he al e na i e use o he sodium sal as a me alla ing
agen , ec ys alliza ion was pe o med o bo h ypes o
mix u es.
C ys al s uc u e o 5
Sui able c ys als o mix u e A we e g own om a chlo o o m
solu ion, labelled 5. The c ys al s uc u e o 5(Fig. 2 and
Table 1) consis s o molecules wi h he palladium(II) a om
Scheme 3 Reac ion sequence leading o he compounds wi h diphosphine.
Dal on T ansac ions Pape
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bonded in a sligh ly dis o ed squa e-plana en i onmen o
wo mu ually pe pendicula pai s o [O,O] and [N,S] dono s,
pe aining o b idging ace a e and chela ing 2- hiome hyl-
anilide ligands, espec i ely; he ni ogen a oms in u n ac as
b idging dono s be ween wo palladiums. The ni ogen a oms
a e a anged in a squa e-plana geome y and in u n ac as
b idging dono s holding he palladium a oms a a midway dis-
ance be ween each pai o ni ogens o gi e an eigh -mem-
be ed ing o al e na ing Pd/N cen e s. Thus, he palladium
coo dina ion planes a e se as wo pai s o mu ually acing pa -
allel planes ca. 90° o he Pd
4
N
4
ing.
We easoned ha mix u e B should p oduce ei he c ys-
als o 2a–2c, as app op ia e, o a s uc u e analogous o 5
depending on whe he o no he ace a e ligands we e los
in he co esponding p epa a ion. Again, he expe imen al
ac s show ha an absolu ely dis inc i e s uc u e was
ob ained: a inuclea c ys al oid o any ace a e ligands,
labelled 6.
C ys al s uc u e o 6
Sui able c ys als we e g own om mix u e B om a DMSO-d
6
solu ion, labelled 6. The c ys al s uc u e (Fig. 3 and Table 1)
consis s o a inuclea molecule wi h a cen al Pd
3
N
3
six-mem-
be ed ing o al e na ing palladium and ni ogen a oms in a
chai con o ma ion, wi h he Pd(2) and N(10) a oms poin ing
o opposi e di ec ions om he Pd(1)N(8)N(9)Pd(3) plane
(Fig. 5b). Each palladium a om is bonded o a chela ing biden-
a e [N,S] 2- hiome hylanilide, ha in u n also coo dina es as
a b idging ligand be ween wo me al a oms ia he ni ogen
dono . The ou h coo dina ion si e a each palladium is occu-
pied by a chlo ide ligand ans o ni ogen o he h ee me al
cen e s. The palladium coo dina ion planes [S(1)N(8)Cl(1)Pd
(1)N(10)] (plane 1), [S(2)N(8)Cl(2)Pd(2)N(9)] (plane 2) and [S(3)
N(9)Cl(3)Pd(3)N(10)] (plane 3) a e se as ollows: 1^2 83.44°;
1^3 77.08°; 2^3 79.91°.
In iew o his unexpec ed beha io o he amine ligand
s emming om pa ial hyd olysis o he pa en Schiffbase,
we sough ou o s udy he beha io o ee 2-me hyl-
hioaniline i sel in o de o de e mine i compounds 5and
6we e p oduced only om he co esponding palladacycles,
o i i was solely dependen on he p esence o he ee
amine. Fo such a pu pose 2- hiome hylaniline was ea ed
independen ly wi h Pd(OAc)
2
in oluene o wi h Na
2
[PdCl
4
]
in me hanol (see Scheme 2 and Expe imen al o p epa a i e
de ails).
The o me p ocess ga e only he ee amine, as was de e -
mined by
1
H NMR spec oscopy. Howe e , in he la e case
he
1
H NMR spec um shows he e a e wo single s assignable
o he SMe g oups and wo se s o a oma ic peaks con aining
ou double s and ou iple s in ag eemen wi h a ou -spin
sys em o an o ho-subs i u ed phenyl ing. This is a diffe ing
si ua ion om ha ound o compounds 5and 6, whe e he
Table 1 C ys allog aphic da a o 1b,5–8
Compound 1b 5 6 7 8
Empi ical o mula C
16
H
16
ClNOPdS C
17
H
20
Cl
4
N
2
O
6
Pd
2
S
2
C
25
H
36
Cl
3
N
3
O
2
Pd
3
S
5
C
31
H
35
Cl
13
N
4
Pd
4
S
4
C
78
H
66
Cl
2
N
2
O
22
PdPd
3
S
2
W
2
Fo mula weigh 412.245 767.131 996.518 1479.647 2329.12
Tempe a u e/K 100.0 100.0 100.0 100.00 100.0
C ys al sys em Monoclinic T iclinic Monoclinic O ho hombic T iclinic
Space g oup P2
1
/cP1
ˉP2
1
/n Pbca P1
ˉ
a/Å 8.1340(2) 11.6987(6) 9.6057(5) 10.6947(8) 10.8665(13)
b/Å 11.6466(3) 15.0875(8) 19.0596(10) 22.0850(16) 12.0797(14)
c/Å 17.0711(4) 18.3377(9) 19.8471(11) 40.285(3) 19.070(2)
α/° 90 105.262(3) 90 90 72.291(7)
β/° 101.9138(10) 104.871(3) 91.4728(17) 90 89.037(7)
γ/° 90 107.653(4) 90 90 78.172(7)
Volume/Å
3
1582.37(7) 2769.0(3) 3632.4(3) 9515.0(12) 2331.2(5)
Z44 4 81
ρ
calc.
/g cm
−3
1.730 1.840 1.822 2.066 1.659
μ/mm
−1
1.471 15.748 2.006 2.425 3.262
F(000) 821.5 1518.5 1961.1 5733.3 1136
C ys al size/mm
3
0.156 × 0.127 × 0.092 0.08 × 0.03 × 0.02 0.14 × 0.09 × 0.05 0.09 × 0.07 × 0.03 0.200 × 0.090 × 0.030
Radia ion Mo Kα(λ= 0.71073) Cu Kα(λ= 1.54178) Mo Kα(λ= 0.71073) Mo Kα(λ= 0.71073) Mo Kα(λ= 0.71073)
2θ/° 4.88 o 77.14 6.62 o 140.14 4.74 o 56.76 4.32 o 56.68 1.810 o 26.445
Index anges −14 ≤h≤14, −20
≤k≤19, −29 ≤l≤
29
−14 ≤h≤14,
−18 ≤k≤18,
−22 ≤l≤22
−12 ≤h≤12,
−25 ≤k≤25,
−25 ≤l≤26
−14 ≤h≤14,
−29 ≤k≤29,
−33 ≤l≤53
−13 ≤h≤13,
−15 ≤k≤15,
−23 ≤l≤23
Re lec ions collec ed 63 757 68 334 86 053 98 993 70 681
Independen e lec ions 8909 [R
in
= 0.0353,
R
sigma
= 0.0233] 10 523 [R
in
= 0.1983,
R
sigma
=0.1049] 9079 [R
in
= 0.0378,
R
sigma
= 0.0198] 11 826 [R
in
= 0.0686,
R
sigma
= 0.0392] 9506 [R
in
= 0.1012]
Da a/ es ain s/pa ame e s 8909/0/193 10 523/0/602 9079/24/459 11 826/24/574 9506/439/550
Goodness-o - i on F
2
1.037 1.020 1.050 1.045 1.087
Final Rindexes [I≥2σ(I)] R
1
= 0.0232,
wR
2
= 0.0510 R
1
= 0.0676,
wR
2
= 0.1638 R
1
= 0.0328,
wR
2
= 0.0737 R
1
= 0.0727,
wR
2
= 0.1316 R
1
= 0.0762,
wR
2
= 0.1540
Final Rindexes [all da a] R
1
= 0.0312,
wR
2
= 0.0547 R
1
= 0.1213,
wR
2
= 0.2051 R
1
= 0.0370,
wR
2
= 0.0764 R
1
= 0.0832,
wR
2
= 0.1368 R
1
= 0.1130,
wR
2
= 0.1649
La ges diff. peak/hole/e Å
−3
0.73/−1.16 1.59/−1.82 3.16/−2.83 1.63/−1.91 2.303/−2.307
Pape Dal on T ansac ions
9686 |Dal on T ans.,2024,53, 9680–9691 This jou nal is © The Royal Socie y o Chemis y 2024
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2- hiome hylanilide ligands we e in equi alen chemical
en i onmen s, poin ing o wo ypes o non-equi alen amine
molecules ha a e p esen in he inal compound. Fo una ely,
single-c ys als could be ob ained o cla i y his inding and he
esul is e en mo e ascina ing han o s uc u es 5and 6
( ide in a).
C ys al s uc u e o 7
Sui able c ys als we e g own om a chlo o o m solu ion,
labelled 7. The c ys al s uc u e (Fig. 4 and Table 1) consis s o
ou palladium a oms, ou chlo ide and ou 2- hiome hyl-
anilide ligands displayed such ha he e a e h ee ypes o pal-
ladium coo dina ion en i onmen s: 2 + 1 + 1. The aniline moi-
e ies a e linked o he Pd(1), Pd(2) and Pd(4) a oms in a biden-
a e [N,S] ashion and he ou palladium a oms a e bonded
oge he ia he ni ogen om b idging 2-MeC
6
H
4
NH
2
-Nuni s;
he chlo ine a oms comple e he coo dina ion sphe e a he
me al as e minal ligands. Thus, Pd(1) is bonded o wo chela -
ing [N,S] aniline ligands wi h he dono a oms in a cis geome-
y; Pd(2) and Pd(4) o one chela ing amine, a e minal chlo -
ine a om and a ni ogen a om om an adjacen o ganic
ligand; Pd(3) o wo mu ually ans e minal chlo ine a oms
and wo ni ogen dono s o m nea by amine ligands also in a
ans a angemen . All o which esul s in a Pd
4
N
4
eigh -mem-
be ed ing o al e na ing palladium and ni ogen a oms. The
palladium coo dina ion planes [Pd(1)N(1)N(4)S(1)S(4)] (1), [Pd
(2)N(1)N(2)S(2)Cl(1)] (2), [Pd(3)N(2)N(3)Cl(2)Cl(3)] (3) [Pd(4)N
(3)N(4)S(3)Cl(4)] (4) [1^2 89.59°; 1^3 87.60°, 1^4 86.55°, 2^3
85.92°; 3^4 85.81°; 2^4 8.99°] a e angled ca. 90°, sa e o
planes 2 and 4 which a e close o a pa allel disposi ion.
Nex , we a emp ed o s udy he beha io o he 1a–1 class
complexes wi h diphosphines o de e mine whe he hey
would gi e species analogous o he hiosemica bazone-[C,N,S]
palladacycles we ha e desc ibed in he pas , i.e., complexes
wi h a mono-coo dina ed diphosphine and also he ensuing
dinuclea compounds wi h he diphosphine ligand b idging
wo me al cen e s; o i al e na i ely, and gi en he esul s
depic ed abo e, hey would e ol e o unp eceden ed mul inuc-
lea compounds; o which pu pose we chose compound 1d
and he diphosphine dppm, Ph
2
PCH
2
PPh
2
.
Hence, ea men o 1d wi h dppm in 1 : 1 mola a io and
NaClO
4
ga e he hoped o complex 3d asapu eai -s ablesolid,
which was ully cha ac e ized. The
31
P NMR spec um displayed
wo double s a −23.6 and 31.3 ppm, o he wo inequi alen
phospho us nuclei. The esonance a lowe equency was
assigned o he non-coo dina ed phospho us nucleus; whe eas he
one a highe equency was assigned o he phospho us nucleus
bonded o palladium. The HC N esonance was a double
coupled o he ans phospho us nucleus (
4
J(HiP) = 8.4 Hz). Bo h
he MeOandSMe esonances we e shi ed o lowe equency ca.
0.6 and 0.7 ppm espec i ely, due o shielding by he phosphine
phenyl ings. The p o on signal was an appa en iple om he
AA′XX′ ou spin sys em P(CH
2
)Pwi h an N alue o 2.4 Hz.
A emp s o p epa e he he e obime allic complex 4d by ea men
o 3d wi h [W(CO)
5
(THF)] ga e an un ea able mix u e which was
no u he in es iga ed. Likewise, eac ion o 3d wi h o he sub-
s a es bea ing labile ligands such as [Fe(CO)
4
(THF)] and [Pd
(Cl)
2
(PhCN)
2
], o yield he co esponding dinuclea species we e
also deemed unsuccess ul. Al e na i ely, eac ion o 1d wi h [W
(CO)
5
{Ph
2
PCH
2
PPh
2
–P}] did p oduce he expec ed compound 4d
Fig. 1 ORTEP d awing o compound 1b wi h he mal ellipsoid plo
shown a 50% p obabili y le el. Hyd ogen a oms and sol en molecules
ha e been omi ed o cla i y. Selec ed bond dis ances (Å) and angles (°):
Pd(1)–C(1) 1.9936(11), Pd(1)–N(1) 2.0039(9), Pd(1)–S(1) 2.3987(3), Pd(1)–
Cl(1) 2.2963(3), S(1)–Pd(1)–Cl(1) 98.815(10), N(1)–Pd(1)–S(1) 84.63(3),
N(1)–Pd(1)–Cl(1) 175.43(3), C(1)–Pd(1)–S(1) 166.53(3), C(1)–Pd(1)–Cl(1)
94.65(3), C(1)–Pd(1)–N(1) 81.91(4).
Fig. 2 ORTEP d awing o compound 5wi h he mal ellipsoid plo
shown a 50% p obabili y le el. Hyd ogen a oms and sol en molecules
ha e been omi ed o cla i y. Selec ed bond dis ances (Å) and angles (°):
Pd(01)–S(005) 2.262(3), Pd(01)–N(00N) 2.065(8), Pd(01)–N(00M)
2.032(9), Pd(01)–O(00I) 2.042(8), N(00N)–Pd(01)–S(005) 99.5(3),
N(00N)–Pd(01)–O(00I) 88.1(3), N(00M)–Pd(01)–O(00I) 87.0(3), N(00M)–
Pd(01)–S(005) 85.7(3); Pd(02)–O(00G) 2.044(8), Pd(02)–N(00N)
2.014(9), Pd(02)–N(00M) 2.063(9), Pd(02)–S(006), 2.257(3), N(00N)–
Pd(02)–S(006) 86.2(3), N(00N)–Pd(02)–O(00G) 91.2(4), N(00M)–
Pd(02)–O(00G) 88.4(3), N(00M)–Pd(02)–S(006) 94.4(3).
Dal on T ansac ions Pape
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