Bridge cleavage of transition metal dimers by chelating S,N ligands. X-ray crystal structure of [Pd{SPPh2N=C (NH2)NH-S,N}(η3-C3H5)]

Article abstract of DOI:10.1016/S0277-5387(01)00738-0

Deprotonation of the N-thiophosphoryl compounds Me₂P(S)N=C(NH₂)₂ (HL¹), Ph₂P(S)N=C(Me)(NH₂) (HL²) or Ph₂P(S)N=C(NH₂)₂ (HL³) using potassium t-butoxide in thf, followed by treatment with [Rh(μ-Cl)(η⁴-cod)]₂ (cod =1,5-cis,cis-cyclooctadiene), [Pd(μ-Cl)(η³-C₃H₅)]2 or [RhCl(μ-Cl)(η⁵-C₅Me₅)]2 affords [Rh(Lⁿ-S,N)(η⁴-cod)] 1-3, [Pd(Lⁿ-S,N)(η³-C₃H₅)] 4-6 and [RhCl(Lⁿ-S,N)(η₅-C₅Me₅)] 7-9, respectively. The (Lⁿ)- anions form six-membered S,N chelate rings at the metal centre, in a manner analogous with β-diketonates and imidodiphosphinates. The complexes 1-9 have been characterised spectroscopically and by single crystal X-ray diffraction for [Pd(L³-S,N)(η³-C₃H₅)] 6. The molecular structure of 6 confirms S,N chelation of the (L³)- anion to give a palladacycle adopting a half boat conformation.

Full text of DOI:10.1016/S0277-5387(01)00738-0

Polyhedron 20 (2001) 1831–1835
www.elsevier.com/locate/poly
Bridge cleavage of transition metal dimers
by chelating S,N ligands.
X-ray crystal structure of [Pd{SPPh2NꢀC(NH2)NH-S,N}(h3-C3H5)]
Pravat Bhattacharyya, Alexandra M.Z. Slawin, J. Derek Woollins *
Department of Chemistry, Uni6ersity of St Andrews, St Andrews, Fife KY16 9ST, Scotland, UK
Received 30 October 2000; accepted 29 January 2001
Abstract
Deprotonation of the N-thiophosphoryl compounds Me2P(S)NꢀC(NH2)2 (HL1), Ph2P(S)NꢀC(Me)(NH2) (HL2) or
Ph2P(S)NꢀC(NH2)2 (HL3) using potassium t-butoxide in thf, followed by treatment with [Rh(m-Cl)(h4-cod)]2 (cod=1,5-cis,cis-cy-
clooctadiene), [Pd(m-Cl)(h3-C3H5)]2 or [RhCl(m-Cl)(h5-C5Me5)]2 affords [Rh(Ln-S,N)(h4-cod)] 1–3, [Pd(Ln-S,N)(h3-C3H5)] 4–6
and [RhCl(Ln-S,N)(h5-C5Me5)] 7–9, respectively. The (Ln)− anions form six-membered S,N chelate rings at the metal centre, in
a manner analogous with b-diketonates and imidodiphosphinates. The complexes 1–9 have been characterised spectroscopically
and by single crystal X-ray diffraction for [Pd(L3-S,N)(h3-C3H5)] 6. The molecular structure of 6 confirms S,N chelation of the
(L3)− anion to give a palladacycle adopting a half boat conformation. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Palladium; Rhodium; Thiophosphoryl guanidines; X-ray crystal structure
of Me2P(S)NꢀC(NH2)2 (HL1), Ph2P(S)NꢀC(Me)(NH2)
1. Introduction
(HL2) or Ph2P(S)NꢀC(NH2)2 (HL3) (Fig. 1), in which
(Ln)− forms six membered S,N chelate rings at platinu-
Imidodiphosphinate anions [R2P(E)NP(E%)R%2] (R,
R%=alkyl, aryl or alkoxy; E, E%=O, S or Se) have
received substantial attention in recent years, finding
usage in applications such as metal extraction agents,
m(II) [17]. This reactivity is comparable to that of
[(EPPh2)2N]− (E=S or Se), which generates cis-
[Pt{(EPPh2)2N-E,E%}(PR3)2]Cl [18,19], although the
combination of sulphur and nitrogen donor atoms sup-
NMR shift reagents and in catalytic functions [1–8].
plied by (Ln)− is unmatched amongst imidodiphosphi-
We are currently investigating the chemistry of struc-
nates. Structural similarities are also evident between
turally similar phosphorus(V) derivatised guanidines
HLn and 1-amidino-2-thioureas RNHC(S)-NꢀC(NH2)2
and amidines R2P(E)NꢀC(X)(NH2) (R=alkyl or aryl;
(RꢀH or alkyl), the anions of which form S,N chelates
E=oxygen or sulphur; X=NH2 or alkyl). These
[20] and, in a recent example, act as scaffolds for
molecules, readily available from [R2P(E)(NCN)]− [9–
heterometallic cage synthesis [21].
16], possess an ionisable nitrogen-bound proton and
have the capacity for delocalisation of the resulting
uninegative charge through the p-system of the
[R2P(E)NꢀC(X)(NH)]− anion; hence they could func-
tion as E,N-bidentate ligands in a manner analogous
with imidodiphosphinates. We have previously pre-
pared cis-[Pt(Ln-S,N)(PR3)2]Cl (PR3ꢀPMe2Ph or 1/
2dppe) from cis-[PtCl2(PR3)2] and the potassium salts
* Corresponding author. Tel.: +44-1334-463181; fax: +44-1334-
463384.
Fig. 1. Structures of HL1–3
.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00738-0

1832
P. Bhattacharyya et al. / Polyhedron 20 (2001) 1831–1835
[Ph2P(O)NP(E)Ph2]− exhibit a m2E-bridging geometry
in [Pd(h3-C3H5){Ph2P(O)NP(E)Ph2-E}]2 [19,22,23].
Complexes 1–9 are air and moisture stable with high
solubility in chlorinated solvents, selected spectroscopic
data are presented in Table 1. The FAB+ mass spectra
contain an intense peak from the molecular ion for 1–6
and [M+−Cl] for 7–9. The 31P{1H} NMR shows a
shift to low frequency by approximately 10–20 ppm
from the free ligand value upon deprotonation and
coordination, comparable with coordination shifts gen-
erally noted in [(EPPh2)2N]− complexes [5,18,19,23].
2
For 1–3 J(RhꢁP) is 4 Hz, however this coupling is
unresolved for 7–9. In their IR spectra, 1–9 give bands
of medium intensity between 3460–3120 cm−1 due to
w(NH, NH2), essentially unchanged from HLn (3437–
3142 cm−1) and strong absorptions at 1630–1480
cm−1 from w(CN) and l(NH) vibrations of (Ln)−. The
w(PS) bands for the (L1)− complexes 1, 4 and 7 (561,
553 and 562 cm−1, respectively) are 30–40 cm−1 below
Fig. 2. Structures of complexes 1–9.
We describe here the synthesis of [Rh(Ln-S,N)(h4-
cod)], [Pd(Ln-S,N)(h3-C3H5)] and [RhCl(Ln-S,N)(h5-
C5Me5)] and the X-ray crystal structure of [Pd(L3-S,N)-
(h3-C3H5)].
those for the (L2,3 −
(583–600 cm−1).
)
complexes 2, 3, 5, 6, 8 and 9
In the 1H NMR, the amine protons of 1–9 give
broad singlets between 3.6–6.1 ppm, cf. 6.1 for HL1,
8.2 and 5.8 for HL2, 5.7 for HL3. Notably, l(NH) in
the (L2)− complexes 2, 5 and 8 (l 4.74, 6.06 and 5.49,
respectively) is approximately 1 ppm to high frequency
2. Results and discussion
We have previously shown that HLn are deproto-
nated by potassium t-butoxide to give anions (Ln)−
which react with cis-[PtCl2(PR3)2] (PR3=PMe2Ph or
1/2dppe), giving cis-[Pt(Ln-S,N)(PR3)2]Cl [17]. By a sim-
ilar method, (Ln)− reacts with [Rh(m-Cl)(h4-cod)]2,
[Pd(m-Cl)(h3-C3H5)]2 or [RhCl(m-Cl)(h5-C5Me5)]2 to
give [Rh(Ln-S,N)(h4-cod)] 1–3, [Pd(Ln-S,N)(h3-C3H5)]
4–6 and [RhCl(Ln-S,N)(h5-C5Me5)] 7–9 (Fig. 2), with
by-production of KCl. Conversion is quantitative by
31P{1H} NMR, isolated yields are 40–70%. Com-
pounds 1–9 are isostructural with those obtained when
[(EPPh2)2N]−, E=S or Se, cleave the chloro-bridged
precursors although the mixed donor ligands
of the values in the (L1,3 −
mately 3.6 for 1 and 3, approximately 4.9 for 4 and 6,
4.33 (7) and 4.79 (9)]. The NH2 resonance of (L1,3 −
)
complexes [l(NH) approxi-
)
appears to low frequency of NH for 1 and 3, the order
is reversed in 4 and 6; a similar alternation occurs
between 7 and 9. In 2, 5 and 8 the methyl protons of
4
the amidinate moiety show a J(HNCCH) coupling of
2 Hz, as seen in uncomplexed HL2 (2 Hz).
The molecular structure of [Pd(L3-S,N)(h3-C3H5)] 6
(Fig. 3) confirms that (L3)− is S,N-bidentate, forming a
PdꢁSꢁPꢁNꢁCꢁN palladacycle with an h3-allyl group
Table 1
Selected spectroscopic data [31P{1H} NMR, IR and FAB+ MS] for HL1–3 and 1–9
a,b
31P{1H} lP
IR (cm−1) w(NH, NH2)
w(PS)
FAB+ MS c M+
HL1 Me2P(S)NꢀC(NH2)2
HL2 Ph2P(S)NꢀC(Me)(NH2)
HL3 Ph2P(S)NꢀC(NH2)2
1 [Rh(L1-S,N)(h4-cod)]
48.3
42.2
42.5
38.9(4)
31.0(4)
35.3(4)
37.6
28.9
34.0
3377, 3142
558
575
275
553
592
600
561
589
591
562
583
585
151
274
3361, 3285, 3230
3437, 3350, 3299, 3201 586
3389, 3287, 3178
3321
3415, 3287, 3173
3460, 3340, 3122
3346
3399, 3304, 3169
3309, 3166
3245
362
485
486
298
420
422
388
511
512
2 [Rh(L2-S,N)(h4-cod)]
3 [Rh(L3-S,N)(h4-cod)]
4 [Pd (L1-S,N)(h3-C3H5)]
5 [Pd (L2-S,N)(h3-C3H5)]
6 [Pd (L3-S,N)(h3-C3H5)]
7 [RhCl(L1-S,N)(h5-C5Me5)]
8 [RhCl(L2-S,N)(h5-C5Me5)]
9 [RhCl(L3-S,N)(h5-C5Me5)]
36.1
22.9
28.2
3474, 3297, 3172
a Spectra in CDCl3 for HL1,2 and 1–9, CD3OD for HL3.
b 2J(RhꢁP) in parentheses for 1–3, no coupling resolved in 7–9.
c [M+−Cl] for 7–9.

P. Bhattacharyya et al. / Polyhedron 20 (2001) 1831–1835
1833
Elmer System 2000 spectrometers, respectively, elemen-
tal analyses and FAB+ mass spectra (3-NOBA matrix)
were by the University of St Andrews Microanalytical
Service and EPSRC National Mass Spectrometry Ser-
vice Centre, Swansea. Selected spectroscopic data for
HL1–3 and 1–9 are given in Table 1.
3.1. [Rh(Ln-S,N)(p4-cod)] (L1=1, L2=2, L3=3)
To HLn (0.24 mmol) and potassium t-butoxide (0.3
mmol) in thf (3 cm3) was added [Rh(m-Cl)(h4-cod)]2
(0.12 mmol) in one portion and the orange solution
stirred for 2 h. The solvent was removed in vacuo, the
product extracted into dichloromethane (5 cm3) and
filtered through celite. Addition of hexane (50 cm3)
gave 1–3 as yellow microcrystalline solids.
Fig. 3. X-ray crystal structure of [Pd(L3-S,N)(h3-C3H5)] 6 (hydrogen
,
atoms omitted for clarity). Selected bond lengths (A) and angles (°):
Pd(1)ꢁN(14) 2.085(3), Pd(1)ꢁS(1) 2.3536(10), Pd(1)ꢁC(14) 2.137(4),
Pd(1)ꢁC(15) 2.097(4), Pd(1)ꢁC(16) 2.151(4), S(1)ꢁP(1) 2.0167(12),
P(1)ꢁN(1) 1.601(2), N(1)ꢁC(13) 1.348(4), C(13)ꢁN(14) 1.321(4),
C(13)ꢁN(13) 1.368(4); S(1)ꢁPd(1)ꢁN(14) 99.00(8), Pd(1)ꢁS(1)ꢁP(1)
99.76(4), S(1)ꢁP(1)ꢁN(1) 119.88(10), P(1)ꢁN(1)ꢁC(13) 122.9(2),
Compound 1. Anal. Found: C, 36.4; H, 6.0; N, 11.9.
Calc. for C11H21N3PSRh: C, 36.6; H, 5.9; N, 11.6%. lH:
4.01 (m, 4H, C8H12), 3.81 (br s, 2H, NH2), 3.62 (br s,
1H, NH), 2.41 (m, 4H, C8H12), 1.88 (m, 4H, C8H12),
N(1)ꢁC(13)ꢁN(14)
125.4(3),
C(13)ꢁN(14)ꢁPd(1)
127.9(2),
N(1)ꢁC(13)ꢁN(13) 113.8(3), N(13)ꢁC(13)ꢁN(14) 120.7(3).
2
1.83 (d, 6H, JPH=13 Hz, CH3).
completing the coordination sphere. The internal NꢁC
and PꢁN distances [N(14)ꢁC(13) 1.321(4), C(13)ꢁN(1)
Compound 2. Anal. Found: C, 55.6; H, 5.1; N, 5.5.
Calc. for C22H27N2PSRh: C, 54.4; H, 5.6; N, 5.8%. lH:
7.88 (m, 4H, C6H5), 7.35 (m, 6H, C6H5), 4.74 (br s, 1H,
NH), 4.08 (m, 2H, C8H12), 3.65 (m, 2H, C8H12), 2.25
(m, 4H, C8H12), 2.13 (d, 3H, JHH=2 Hz, CH3), 1.80
(m, 4H, C8H12).
Compound 3. Anal. Found: C, 50.3; H, 4.9; N, 8.0.
Calc. for C21H25N3PSRh: C, 51.9; H, 5.2; N, 8.7%. lH:
7.93 (m, 4H, C6H5), 7.42 (m, 6H, C6H5), 4.16 (br s, 2H,
NH2), 4.11 (m, 2H, C8H12), 3.70 (m, 2H, C8H12), 3.63
(br s, 1H, NH), 2.29 (m, 4H, C8H12), 1.84 (m, 4H,
C8H12).
,
1.348(4), P(1)ꢁN(1) 1.601(2) A] of the PdꢁSꢁPꢁNꢁCꢁN
ring are, within experimental error, unchanged from
cis-[Pt(L2-S,N)(PMe2Ph)2]Cl, with P(1)ꢁS(1) [2.0167(12)
4
,
A] marginally shorter than in the platinum complex
,
[2.036(4) A] [17]. The MꢁSꢁP, SꢁMꢁN and SꢁPꢁN
angles of 6 [99.76(4), 99.00(8) and 119.88(10)°] are
substantially
enlarged
compared
with
cis-
[Pt(L2)(PMe2Ph)2]Cl [91.75(12), 90.8(3) and 115.3(3)°],
whereas the MꢁNꢁC angle [127.9(2)°] is smaller than
the platinum complex [134.5(7)°]. Within the chelate,
the N(14)ꢁPd(1)ꢁS(1)ꢁP(1) chain has a mean deviation
3.2. [Pd(Ln-S,N)(p3-C3H5)] (L1=4, L2=5, L3=6)
,
from planarity of 0.01 A, N(1) and C(13) lie 0.82 and
,
0.59 A, respectively below this plane. This contrasts
with cis-[Pt(L2-S,N)(PMe2Ph)2]Cl in which only the sul-
To HLn (0.50 mmol) and potassium t-butoxide (0.55
mmol) in thf (5 cm3) was added [Pd(m-Cl)(h3-C3H5)]2
(0.25 mmol) in one portion and the yellow solution was
stirred for 2 h. The solvent was removed in vacuo, the
product extracted into dichloromethane (5 cm3) and
filtered through Celite. Addition of hexane (50 cm3)
gave the products as brown (4), orange (5) or yellow (6)
solids.
,
phur atom is displaced (by 1.27 A) from the platinacy-
cle plane; the (Ln)− backbone appears to have the same
conformational freedom available to [(EPR2)2N]−.
In summary, cleavage of chloro-bridged bimetallic
complexes is readily accomplished using anions derived
from phosphorus(V) guanidines and amidines, with the
formation of the six-membered chelate rings analogous
to b-diketonates and imidodiphosphinate ligands.
Compound 4. Anal. Found: C, 24.2; H, 3.9; N, 13.0.
Calc. for C6H14N3PSPd: C, 24.2; H, 4.7; N, 14.1%. lH:
5.24 (m, 1H, C3H5), 4.96 (br s, 1H, NH), 4.24 (br s, 2H,
3
3. Experimental
NH2), 3.85 (d, 1H, JHH=6 Hz, C3H5), 3.56 (d, 1H,
3
3JHH=6 Hz, C3H5), 2.90 (d, 1H, JHH=12 Hz, C3H5),
3
2
Complexations were performed under dinitrogen,
work-ups were carried out in air. Thf was distilled from
Na-benzophenone ketyl, Rh2 and Pd2 precursors were
prepared by literature procedures [24–26], other sol-
2.53 (d, 1H, JHH=12 Hz, C3H5), 1.78 (d, 3H, JPH
=
2
12 Hz, CH3), 1.72 (d, 3H, JHH=12 Hz, CH3).
Compound 5. Anal. Found: C, 47.5; H, 4.3; N, 6.2.
Calc. for C17H19N2PSPd: C, 48.5; H, 4.5; N, 6.7%. lH:
7.93 (m, 4H, C6H5), 7.30 (m, 6H, C6H5), 6.06 (br s, 1H,
NH), 5.1 (m, 1H, C3H5), 3.75 (d, 1H, 3JHH=7 Hz,
1
vents and reagents were as supplied. 31P{1H} and H
NMR (121.4 and 300.0 MHz, CDCl3) and IR spectra
(KBr discs) were on Varian Gemini 2000 and Perkin–
3
C3H5), 3.61 (d, 1H, JHH=6 Hz, C3H5), 2.76 (d, 1H,

1834
P. Bhattacharyya et al. / Polyhedron 20 (2001) 1831–1835
3JHH=12 Hz, C3H5), 2.54 (d, 1H, 3JHH=12 Hz, C3H5),
2.22 (d, 3H, JHH=2 Hz, CH3).
5. Supplementary material
4
Compound 6. Anal. Found: C, 44.4; H, 4.1; N, 9.7.
Calc. for C16H18N3PSPd: C, 45.6; H, 4.3; N, 10.0%. lH:
7.90 (m, 4H, C6H5), 7.42 (m, 6H, C6H5), 5.14 (m, 1H,
C3H5), 4.98 (br s, 1H, NH), 4.49 (br s, 2H, NH2), 3.74
(br s, 1H, C3H5), 3.70 (br s, 1H, C3H5), 2.80 (d, 1H,
3JHH=11 Hz, C3H5), 2.56 (d, 1H, 3JHH=11 Hz, C3H5).
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 151583 for compound 6.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
3.3. [RhCl(Ln-S,N)(p5-C5Me5)] (L1=7, L2=8,
L3=9)
To HLn (0.3 mmol) and potassium t-butoxide (0.35
mmol) in thf (5 cm3) was added [RhCl(m-Cl)(h5-
C5Me5)]2 (0.15 mmol) in one portion and the red mix-
ture stirred for 24 h. The products 7 and 9 precipitate
from thf as orange-brown solids; for 8 the solution was
reduced to dryness in vacuo, the crude product ex-
tracted into dichloromethane (5 cm3), filtered through
Celite and precipitated with hexane (50 cm3) to give 8
as a brown solid.
Acknowledgements
We are grateful to the EPSRC for funding (P.B.),
JREI for an equipment grant, Johnson Matthey plc for
the loan of precious metals and to Professor Alfred
Schmidpeter (University of Munich) for the generous
gift of samples of HL1–3
.
Compound 7. Anal. Found: C, 36.9; H, 5.8; N, 9.9.
Calc. for C13H24N3PSRhCl: C, 36.8; H, 5.7; N, 9.9%.
lH: 4.66 (br s, 2H, NH2), 4.33 (br s, 1H, NH), 1.68 (d,
References
2
6H, JPH=13 Hz, PCH3), 1.57 (s, 15H, C5Me5).
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(1999) 4152.
Compound 8. Anal. Found: C, 53.7; H, 5.6; N, 4.9.
Calc. for C24H29N2PSRhCl: C, 52.7; H, 5.3; N, 5.1%.
lH: 7.92 (m, 4H, C6H5), 7.37 (m, 6H, C6H5), 5.49 (br s,
1H, NH), 2.35 (d, 3H, JHH=3 Hz, CH3), 1.43 (s, 15H,
C5Me5).
Compound 9. Anal. Found: C, 47.9; H, 5.0; N, 6.9.
Calc. for C23H28N3PSRhCl: C, 50.4; H, 5.1; N, 7.7%.
lH: 7.87 (m, 4H, C6H5), 7.35 (m, 6H, C6H5), 4.79 (br s,
1H, NH), 4.59 (br s, 2H, NH2), 1.48 (s, 15H, C5Me5).
4
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4. X-ray crystallography
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519 (2000) 211.
Crystallographic studies on crystals of 6 grown from
dichloromethane–diethyl ether were performed at 293
K on a Bruker SMART diffractometer with graphite-
,
monochromated Mo Ka radiation (u=0.71073 A). The
structure was solved by direct methods, non-hydrogen
atoms were refined with anisotropic displacement
parameters; hydrogen atoms bound to carbon were
,
idealised and fixed (CꢁH 0.95 A), the NH protons
associated with N(13) and N(14) were located by a DF
map and allowed to refine anisotropically. Structural
refinements were by full-matrix least-squares on F2
using the program SHELXTL [27]. C16H18N3PPdS, M=
421.76, monoclinic, space group P21/c, a=14.2943(3),
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,
b=10.7975(1), c=12.3736(2) A, i=114.915(1)°, V=
3
1732.04(5) A , Z=4, Dcalc=1.617 Mg m−3, v (Mo
,
Ka)=1.283 mm−1, F(000)=848, crystal size=0.13×
0.1×0.1 mm3. Of the 7311 measured data, 2467 were
unique (Rint 0.0239) to give R1[I\2|(I)]=0.0255 and
wR2=0.0635.

P. Bhattacharyya et al. / Polyhedron 20 (2001) 1831–1835
1835
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.