Synthesis group 10 polyfluorothiolate mono- and bi-nuclear complexes. Crystal structures of [Ni(SC6HF4)2 and[(dppe)Ni(μ-SC6F5)2Pd (C6F5)2]

Article abstract of DOI:10.1016/S0022-328X(02)01734-5

Complexes of the general formula cis-[M(2,3,5, 6-SC₆HF₄)₂(L-L)] (M = Ni, Pd, Pt; L-L = dppm [bis(diphenylphosphino)methane], dppe [1,2-bis(diphenylphosphino)ethane]) have been synthesized (yield > 75%) by the reaction (1:2) between the corresponding cis-[MCl₂(L-L)] and Tl(SC₆ HF₄). These compounds, when treated with cis- [M(C₆F₅)₂(THF)₂] (M = Pd, Pt; THF = OC₄H₈), quantitatively give rise to homo- or heterobinuclear compounds, (including two pairs of coordination position isomers). All of them have been characterized through IR, NMR and Mass spectrometries. The crystal structures of [Ni(SC₆HF₄)₂(dppe)],[(dppe)Ni(μ- SC₆HF₄)₂Pd(C₆F₅) ₂] and [(dppe)Ni(μ-SC₆F₅) ₂Pd(C₆F₅)₂] have been determined, and the different interfacial π-π interactions between aromatic rings, which depend on the nature of the polyfluorothiolate ring, are analyzed.

Full text of DOI:10.1016/S0022-328X(02)01734-5

Journal of Organometallic Chemistry 663 (2002) 98ꢂ107
/
www.elsevier.com/locate/jorganchem
Synthesis of Group 10 polyfluorothiolate mono- and bi-nuclear
complexes. Crystal structures of [Ni(SC6HF4)2(dppe)], [(dppe)Ni(m-
SC6HF4)2Pd(C6F5)2] and [(dppe)Ni(m-SC6F5)2Pd(C6F5)2]
Miguel A. Uso´n ꢀ, Jesu´s M. Llanos
´ ´ ´
Departamento de Quımica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza, C.S.I.C., E-50009 Zaragoza, Spain
Received 21 May 2002; accepted 19 July 2002
Abstract
Complexes of the general formula cis-[M(2,3,5,6-SC6HF4)2(Lꢀ
no)methane], dppe [1,2-bis(diphenylphosphino)ethane]) have been synthesized (yieldꢀ
corresponding cis-[MCl2(LꢀL)] and Tl(SC6HF4). These compounds, when treated with cis-[M(C6F5)2(THF)2] (Mꢁ
/
L)] (Mꢁ
/
Ni, Pd, Pt; Lꢀ
75%) by the reaction (1:2) between the
Pd, Pt; THFꢁ
/
Lꢁ
/
dppm [bis(diphenylphosphi-
/
/
/
/
OC4H8), quantitatively give rise to homo- or heterobinuclear compounds, (including two pairs of coordination position isomers).
All of them have been characterized through IR, NMR and Mass spectrometries. The crystal structures of [Ni(SC6HF4)2(dppe)],
[(dppe)Ni(m-SC6HF4)2Pd(C6F5)2] and [(dppe)Ni(m-SC6F5)2Pd(C6F5)2] have been determined, and the different interfacial pꢂp
/
interactions between aromatic rings, which depend on the nature of the polyfluorothiolate ring, are analyzed.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Organometallic compounds; pꢂp Interactions; Thiolates; Group 10; Homo- and heterobinuclear; Crystal structures
/
1. Introduction
In our studies [1ꢂ
SC6F5 ligand, we have frequently found interfacial
interactions between aromatic rings, most of them intra-
but sometimes intermolecular. According to Hunter and
compare them with their pentafluorotiophenolato
homologues.
As has repeatedly been shown [2,6,7], the tetrahydro-
furane ligands in the complexes cis-[M(C6F5)2(THF)2]
/
4] about complexes containing the
(Mꢁ
/
Pd, Pt; THFꢁOC4H8) can readily be displaced,
/
and the reaction proceeds with stereoretention, which
makes these complexes especially valuable as reagents
for the synthesis of gem-isomers, provided the avail-
ability of a compound with two potentially bridging
ligands, preferably in a cis-geometry.
Sanders [5] such pꢂp interactions are of a mainly
electrostatic nature and are enhanced by the presence
of polarizing substituents on the rings.
In order to widen the scope of our research, we have
studied the presumably similar 2,3,5,6-SC6HF4 ligand,
and found its interfacial interactions to be markedly
different from those of the SC6F5 ligand.
/
2. Experimental
In this paper, we describe the isolation of compounds
of the type cis-[M(SC6HF4)2(Lꢀ
Lꢁdppm, dppe), and their reaction with the ‘cis-
M?(C6F5)2’ moieties (M?ꢁPd, Pt) to give binuclear
[(LꢀL)M(m-SC6HF4)2M?(C6F5)2] complexes. We also
/
L)] (Mꢁ
/
Ni, Pd, Pt; Lꢀ
/
/
2.1. General procedures
/
/
All reactions were carried out at room temperature
(r.t.) in solvents purified by standard procedures [8]. The
compounds Tl(SC6HF4) [9], [MCl2(dppe)] (Mꢁ
Pd [11], Pt [12]), [MCl2(dppm)] (MꢁPd [11], Pt [12]),
and cis-[M(C6F5)2(THF)2] (MꢁPd, Pt) [13] were pre-
pared by previously published procedures.
/
Ni [10],
/
ꢀ Corresponding author. Tel.: ꢃ
187
E-mail address: mauf@uhu.unizar.es (M.A. Uso´n).
/
34-976-761-189; fax: ꢃ34-976-761-
/
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 7 3 4 - 5

´
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
99
C, H and S analyses were performed with a Carlo
Erba EA 1108 microanalyser. IR spectra were recorded
(C6H5), 790(7%); Mꢀ
(2SC6HF4), 504(29%);
429(38%). FABꢄ: M, 866(5%); Mꢀ
2C6H5), 350(11%).
/
(SC6HF4), 685(100%); Mꢀ
Mꢀ(2SC6HF4ꢃC6H5),
(2SC6HF4ꢃ
/
/
/
(over the range 4000ꢂ
/
250 cmꢄ1) on Perkinꢂ
or 1730 FT spectrophotometers, using Nujol mulls
/Elmer 833
/
/
1
between polyethylene sheets [14]. The H, 19F and 31P
spectra of CDCl3 solutions of the compounds (except
for 14, which had to be dissolved in hexadeuteroace-
tone) were run on Varian UNITY-300 or Bruker ARX-
300 spectrometers; chemical shifts are relative to TMS,
CFCl3 or, respectively, external 85% H3PO4.
Mass spectrometric data were obtained using FABꢃ
and FABꢄ techniques on a VG Autospec apparatus; the
matrix was 3-nitrobenzylalcohol and the samples were
dissolved in CH2Cl2.
2.2.1.3. Compound 3. Yield: 87%. Anal. Found: C,
47.62; H, 2.87; S, 6.67. Calc. for C38H26F8P2PtS2: C,
47.75; H, 2.74; S, 6.71%. IR (cmꢄ1): SC6HF4, n(Cꢀ
/
F)
S) 909vs. H-NMR (d, ppm): CH2,
2.3 (m), SC6HF4, 6.4 (m). 19F-NMR (d, ppm): SC6HF4,
133.1 (m, Fo), ꢄ
142.9 (m, Fm). 31P{1H}-NMR (d,
ppm): 45.8 (t, JPtꢀP
2997 Hz). MS (m/z): FABꢃ: M,
955(8%); Mꢀ(SC6HF4), 774(76%); Mꢀ(C6H5), 879(2%);
Mꢀ(2SC6HF4), 592(6%); Mꢀ(2SC6HF4ꢃC6H5),
516(6%). FABꢄ: M, 955(4%); Mꢀ
(SC6HF4ꢃ2C6H5),
620(3%); Mꢀ(dppeꢃSC6HF4), 375(7%).
1
1219s, 1169vs; n(Cꢀ
/
ꢄ
/
/
ꢁ
/
/
/
/
/
/
/
/
2.2. Syntheses
/
/
2.2.1. General procedure for the synthesis of compounds
2.2.1.4. Compound 4. Yield: 95%. Anal. Found: C,
51.83; H, 2.78; S, 7.29. Calc. for C37H24F8P2PdS2: C,
of the type [M(SC6HF4)2(Lꢀ
Ni (1), Pd (2), Pt (3); LꢀLꢁ
(5))
/
L)] (Lꢀ
/
Lꢁ
/
dppe, Mꢁ
Pd (4), Pt
/
/
/
dppm, Mꢁ
/
52.10; H, 2.84; S, 7.52%. IR (cmꢄ1): SC6HF4, n(Cꢀ
/
F)
S) 909vs; dppm, n(chelate) 538m.
1H-NMR (d, ppm): CH2, 4.1 (t, JPꢀH
10 Hz), SC6HF4,
6.4 (m). 19F-NMR (d, ppm): SC6HF4, ꢄ
132.3 (m, Fo),
142.3 (m, Fm). 31P{1H}-NMR (d, ppm): ꢄ
40.3 (s).
MS (m/z) FABꢃ: M, 851(7%); Mꢀ
(C6H5), 776(9%);
Mꢀ(SC6HF4), 670(100%); Mꢀ(2SC6HF4), 490(24%).
FABꢄ: M, 851(23%); Mꢀ
(dppm), 468(21%); Mꢀ
(2SC6HF4), 491(18%); Mꢀ(2SC6HF4ꢃC6H5), 413(5%).
1218m, 1168s; n(Cꢀ
/
The corresponding dichloro(diphosphino)metal(II)
complex was reacted (1:2) with Tl(SC6HF4), and the
formed TlCl was removed by filtration. The solution
was evaporated to dryness and the residue was repeat-
edly washed with hexane or diethyl ether. A typical
preparation was as follows.
ꢁ
/
/
ꢄ
/
/
/
/
/
/
/
/
/
2.2.1.1. [Ni(SC6HF4)2(dppe)] (1). To an orange sus-
pension of 0.2643 g (0.5 mmol) of [NiCl2(dppe)] in
acetone (15 cm3) was added 0.3859 g (1.0 mmol) of
Tl(SC6HF4). The solution immediately turned red and
an extremely fine, white precipitate was observed.
After 18 h stirring, the formed TlCl was filtered off,
and the solvent was evaporated in vacuo. Hexane (2 ml)
was added and the resulting reddish solid was filtered
off, washed with a further 1 ml of hexane and vacuum
dried. Yield: 78%. Anal. Found: C, 55.56; H, 3.21; S,
7.47. Calc. for C38H26F8NiP2S2: C, 55.70; H, 3.20; S,
2.2.1.5. Compound 5. Yield: 76%. Anal. Found: C,
46.90; H, 2.70; S, 6.98. Calc. for C37H24F8P2PtS2: C,
47.19; H, 2.57; S, 6.81%. IR (cmꢄ1): SC6HF4, n(Cꢀ
/
F)
S) 909vs; dppm, n(chelate)
548s. 1H-NMR (d, ppm): CH2, 4.3 (t, JPꢀH
11,
JPtꢀH
54 Hz), SC6HF4, 6.4 (m). 19F-NMR (d, ppm):
SC6HF4, ꢄ131.9 (d, Fo), ꢄ
142.0 (m, Fm). 31P{1H}-
NMR (d, ppm): ꢄ50.1 (t, JPtꢀP 2575 Hz). MS (m/z)
FABꢃ: M, 941(4%); Mꢀ
(C6H5), 865(4%); Mꢀ
(SC6HF4), 760(100%); Mꢀ(SC6HF4ꢃ2C6H5), 608(4%);
Mꢀ(SC6HF4ꢃdppm), 378(10%); Mꢀ(C6H5ꢃ
1220s, 1191m, 1169s; n(Cꢀ
/
ꢁ
/
ꢁ
/
/
/
/
ꢁ
/
/
/
/
/
7.83%. IR (cmꢄ1): SC6HF4, n(Cꢀ
1188m, 1169m; n(Cꢀ
S) 909vs. 1H-NMR (d, ppm): CH2,
2.2 (m), SC6HF4, 6.4 (m). 19F-NMR (d, ppm): SC6HF4,
133.7 (m, Fo), ꢄ
143.4 (m, Fm). 31P{1H}-NMR (d,
ppm): 56.6 (s). MS (m/z) FABꢃ: M, 819(3%); Mꢀ
(SC6HF4), 637(100%); Mꢀ(C6H5), 741(1%); Mꢀ
(SC6HF4ꢃ2C6H5ꢃ
Ni), 428(8%). FABꢄ: M, 819(3%);
Mꢀ(4C6H5), 512(20%); Mꢀ(2C6H5), 666(3%); Mꢀ
(2C6H5ꢃSC6HF4ꢃNi), 428(14%).
/F) 1233m, 1217m,
/
/
/
/
/
2SC6HF4), 501(7%). FABꢄ: M, 942(100%); Mꢀ
/
(4C6H5),
259(82%).
634(67%);
Mꢀ
/
(4C6H5ꢃ
/
SC6HF4ꢃPt),
/
ꢄ
/
/
/
/
/
2.2.2. General procedure for the synthesis of compounds
of the type [(LꢀL)M(m-SC6HF4)2M?(C6F5)2] (Lꢀ
Lꢁdppe, M?ꢁPd, MꢁNi (6), Pd (7), Pt (8); LꢀLꢁ
dppe, M?ꢁPt, MꢁNi (9), Pd (10), Pt (11); LꢀLꢁ
dppm, M?ꢁPd, MꢁPd (12), Pt (13); LꢀLꢁdppm,
M?ꢁPt, MꢁPd (14), Pt (15))
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.2.1.2. Compound 2. Yield: 88%. Anal. Found: C,
52.10; H, 3.21, S, 7.46. Calc. for C38H26F8P2PdS2: C,
/
/
The necessary bis(tetrafluorothiophenolato)dipho-
sphino-metal(II) complex was treated (1:1) with the
corresponding cis-[M?(C6F5)2(THF)2] species. The sol-
vent was removed and the residue washed with metha-
nol or diethyl ether. A standard preparation is described
below.
52.64; H, 3.02; S, 7.40%. IR (cmꢄ1): SC6HF4, n(Cꢀ
/
F)
S) 908vs. 1H-NMR (d, ppm): CH2,
2.4 (m), SC6HF4, 6.4 (m). 19F-NMR (d, ppm): SC6HF4,
133.6 (m, Fo), ꢄ
143.2 (m, Fm). 31P{1H}-NMR (d,
ppm): 57.5 (s). MS (m/z) FABꢃ: M, 865(5%); Mꢀ
1218m, 1168vs; n(Cꢀ
/
ꢄ
/
/
/

´
100
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
2.2.2.1. [(dppe)Ni(m-SC6HF4)2Pd(C6F5)2] (6). cis-
[Pd(C6F5)2(THF)2] 0.0585 g (0.1 mmol) were added to
SC6HF4ꢃ
2SC6HF4ꢃ
/
3C6H5ꢃ
/
Pt),
Pdꢃ
455(25%);
Pt), 258(15%).
Mꢀ
/
(C6F5ꢃ
/
/
4C6H5ꢃ
/
/
a
red solution of 0.0819
g
(0.1 mmol) of
[Ni(SC6HF4)2(dppe)] in dichloromethane (20 cm3).
After 6 h stirring, the solution was evaporated to
dryness; methanol (1 ml) was added and the red solid
2.2.2.4. Compound 9. Yield: 60%. Anal. Found: C,
44.13; H, 1.93; S, 4.47. Calc. for C50H26F18NiP2PtS2:
C, 44.53; H, 1.94; S, 4.76%. IR (cmꢄ1): C6F5 and
was filtered off, washed with methanol (2ꢅ0.5 ml) and
/
SC6HF4, n(Cꢀ
/
F) 1257s, 1221s, 1174s, 1060vs; n(Cꢀ
/
S)
916vs; n(X-sensitive) 802s, 792s. 1H-NMR (d, ppm):
CH2, 2.3 (m), SC6HF4, 6.5 (m). 19F-NMR (d, ppm):
dried in vacuo, over P2O5. Yield: 72%. Anal. Found: C,
47.21; H, 2.07; S, 5.04. Calc. for C50H26F18NiP2PdS2: C,
47.67; H, 2.08; S, 5.09%. IR (cmꢄ1): C6F5 and SC6HF4,
SC6HF4, ꢄ
120.1 (d, Jom
(m, Fm), ꢄ164.5 (t, Jmp
ppm): 55.2 (s). MS (m/z) FABꢃ: M, 1348(5%); Mꢀ
(C6F5), 1181(7%); Mꢀ(2C6F5ꢃSC6HF4), 833(9%); Mꢀ
(SC6HF4ꢃC6F5), 1000(8%); Mꢀ(2C6F5ꢃSC6HF4ꢃ
Ni), 774(14%); Mꢀ(SC6HF4ꢃ2C6F5ꢃPt), 637(100%).
FABꢄ: M, 1348(8%); Mꢀ
(2C6F5ꢃ2C6H5ꢃNi),
802(12%); Mꢀ(2C6F5ꢃ4C6H5ꢃSC6HF4), 525(55%);
Mꢀ(C6F5ꢃ2SC6HF4ꢃ4C6H5ꢃPtꢃNi), 258(51%).
/
129.9 (m, Fo), ꢄ
23 Hz, JPtꢀF
19 Hz, Fp). 31P{1H}-NMR (d,
/
139.6 (m, Fm); C6F5,
n(Cꢀ
tive) 787m, 777m. H-NMR (d, ppm): CH2, 2.2 (m),
SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4, ꢄ
130.4
(m, Fo), ꢄ140.0 (m, Fm); C6F5, ꢄ116.7 (d, Jom 26 Hz,
Fo), ꢄ165.2 (m, Fm), ꢄ163.2 (t, Jmp 19 Hz, Fp).
31P{1H}-NMR (d, ppm): 54.7 (s). MS (m/z) FABꢃ: Mꢀ
(2C6H5), 1105(5%); Mꢀ(C6F5), 1092(5%); Mꢀ
(SC6HF4), 1078(4%); Mꢀ(2C6F5), 925(16%); Mꢀ
(dppe), 861(9%); Mꢀ(dppeꢃNiꢃSC6HF4), 622(74%);
Mꢀ(2C6F5ꢃ
SC6HF4), 745(33%). FABꢄ: M, 1258(5%);
Mꢀ(dppeꢃNiꢃSC6HF4), 622(100%); Mꢀ(2C6F5ꢃ
SC6HF4ꢃ (2C6F5ꢃSC6HF4ꢃ
3C6H5ꢃNi), (C6F5ꢃ2SC6HF4ꢃ
4C6H5ꢃPdꢃ
/
F) 1222m, 1168m, 1055s; n(Cꢀ
/
S) 913s; n(X-sensi-
ꢄ
/
ꢁ
/
ꢁ
/
445 Hz, Fo), ꢄ166.3
/
1
/
ꢁ
/
/
/
/
/
ꢁ
/
/
/
/
/
/
ꢁ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.2.2.5. Compound 10. Yield: 71%. Anal. Found: C,
42.62; H, 1.81; S, 4.19. Calc. for C50H26F18P2PdPtS2: C,
43.01; H, 1.88; S, 4.59%. IR (cmꢄ1): C6F5 and SC6HF4,
/
3C6H5), 513(19%); Mꢀ
/
/
/
/
455(44%);
Mꢀ
/
/
/
/
/Ni), 259(59%).
n(Cꢀ
/
F) 1222s, 1191m, 1173vs; n(Cꢀ
/
S) 915vs; n(X-
sensitive) 802s, 791s. 1H-NMR (d, ppm): CH2, 2.4
(m), SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4,
2.2.2.2. Compound 7. Yield: 60%. Anal. Found: C,
45.49; H, 1.94; S, 4.89. Calc. for C50H26F18P2Pd2S2: C,
45.93; H, 2.00; S, 4.90%. IR (cmꢄ1): C6F5 and SC6HF4,
ꢄ
/
131.2 (m, Fo), ꢄ
Jom 26 Hz, JPtꢀF
164.6 (t, Jmp
19 Hz, Fp). 31P{1H}-NMR (d, ppm):
58.5 (s). MS (m/z) FABꢃ: M, 1396(7%); Mꢀ
(C6F5),
1228(8%); Mꢀ(2C6F5), 1061(6%); Mꢀ(SC6HF4),
1215(5%); Mꢀ(SC6HF4ꢃ2C6F5), 881(41%); Mꢀ
(2C6F5ꢃSC6HF4ꢃPd), 774(13%); Mꢀ(SC6HF4ꢃ
2C6F5ꢃPt), 685(100%); Mꢀ(C6F5ꢃSC6HF4),
1047(11%). FABꢄ: M, SC6HF4(7%); Mꢀ
(2C6H5),
1240(16%); Mꢀ(2C6H5ꢃ2C6F5), 908(5%); Mꢀ(dppeꢃ
Pdꢃ2SC6HF4), 530(25%); Mꢀ(2C6F5ꢃ4C6H5ꢃ
SC6HF4), 573(5%); Mꢀ(C6F5ꢃ2SC6HF4ꢃ4C6H5ꢃ
PdꢃPt), 259(100%).
/
140.1 (m, Fm); C6F5, ꢄ
/
120.3 (d,
ꢁ
/
ꢁ
/
474 Hz, Fo), ꢄ166.3 (m, Fm),
/
n(Cꢀ
/
F) 1226m, 1168s, 1054s; n(Cꢀ
/
S) 913vs; n(X-
sensitive) 786s, 776s. 1H-NMR (d, ppm): CH2, 2.4
(m), SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4,
ꢄ
/
ꢁ
/
/
/
/
ꢄ
/
131.4 (m, Fo), ꢄ
Jom 33 Hz, Fo), ꢄ165.2 (m, Fm), ꢄ
Hz, Fp). 31P{1H}-NMR (d, ppm): 59.2 (s). MS (m/z)
FABꢃ: Mꢀ
(C6F5), 1140(4%); Mꢀ(2C6F5), 973(10%);
Mꢀ(2C6F5ꢃPd), 867(7%); Mꢀ(2C6F5ꢃSC6HF4ꢃPd),
686(57%); Mꢀ(2C6F5ꢃSC6HF4), 792(47%); Mꢀ
(2C6F5ꢃSC6HF4ꢃ
(dppeꢃPdꢃSC6HF4),
SC6HF4ꢃ3C6H5ꢃPd),
2SC6HF4ꢃ4C6H5ꢃ
/
140.4 (m, Fm); C6F5, ꢄ
/
117.1 (d,
/
/
/
ꢁ
/
/
/
163.2 (t, Jmp
ꢁ
/
19
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
C6H5), 715(12%). FABꢄ: Mꢀ
/
/
/
/
/
/
/
/
/
/
/
622(100%);
455(47%);
Mꢀ
/
(2C6F5ꢃ
/
/
/
/
Mꢀ
/
(C6F5ꢃ
/
/
/
2Pd), 259(26%).
2.2.2.6. Compound 11. Yield: 79%. Anal. Found: C,
39.97; H, 1.78; S, 4.00. Calc. for C50H26F18P2Pt2S2: C,
40.44; H, 1.76; S, 4.32%. IR (cmꢄ1): C6F5 and SC6HF4,
2.2.2.3. Compound 8. Yield: 54%. Anal. Found: C,
42.79; H, 1.73; S, 4.72. Calc. for C50H26F18P2PdPtS2:
C, 43.01; H, 1.88; S, 4.59%. IR (cmꢄ1): C6F5 and
n(Cꢀ
/
F) 1223m, 1174s, 1060vs; n(Cꢀ
/
S) 917vs; n(X-
sensitive) 802m, 792m. 1H-NMR (d, ppm): CH2, 2.2
(m), SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4,
SC6HF4, n(Cꢀ
/
F) 1221s, 1174vs, 1056vs, 1000m; n(Cꢀ
/
S)
916s; n(X-sensitive) 785s, 778s. 1H-NMR (d, ppm):
CH2, 2.2 (m), SC6HF4, 6.5 (m). 19F-NMR (d, ppm):
ꢄ
/
131.1 (m, Fo), ꢄ
Jom 25 Hz, JPtꢀF
164.2 (t, Jmp
20 Hz, Fp). 31P{1H}-NMR (d, ppm):
46.3 (s, Jꢁ
3016 Hz). MS (m/z) FABꢃ: M, 1486(6%);
Mꢀ(C6F5), 1317(11%); Mꢀ(2C6F5), 1150(17%); Mꢀ
(2C6F5ꢃSC6HF4), 969(30%); Mꢀ(2C6F5ꢃSC6HF4ꢃ
Pt), 774(100%); Mꢀ(dppeꢃ
Pt), 892(18%). FABꢄ: M,
1484(6%); Mꢀ(2C6F5ꢃSC6HF4ꢃdppe), 572(8%); Mꢀ
(C6F5ꢃ2SC6HF4ꢃ4C6H5ꢃ2Pt), 258(100%).
/
139.9 (m, Fm); C6F5, ꢄ
/
120.5 (d,
SC6HF4, ꢄ
117.5 (d, Jom
(t, Jmp
19 Hz, Fp). 31P{1H}-NMR (d, ppm): 44.4 (s
JPtꢀP
(2C6F5), 1061(4%); Mꢀ
Mꢀ(2C6F5ꢃSC6HF4ꢃ
SC6HF4ꢃ
Pt), 686(20%). FABꢄ: M, 1396(3%); Mꢀ
(dppeꢃPtꢃSC6HF4), 622(100%); Mꢀ(2C6F5ꢃ
/
131.0 (m, Fo), ꢄ
/
140.3 (m, Fm); C6F5,
ꢁ
/
ꢁ
/
419 Hz, Fo), ꢄ166.1 (m, Fm),
/
ꢄ
/
ꢁ
/
29 Hz, Fo), ꢄ
/
165.2 (m, Fm), ꢄ162.9
/
ꢄ
/
ꢁ
/
ꢁ
/
/
ꢁ
/
3061 Hz). MS (m/z) FABꢃ: M, 1395(3%); Mꢀ
/
/
/
/
/
(2C6F5ꢃ
/
SC6HF4), 881(65%);
/
/
/
/
/
/
/
Pd), 774(100%); Mꢀ
/
(2C6F5ꢃ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

´
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
101
2.2.2.7. Compound 12. Yield: 66%. Anal. Found: C,
45.10; H, 1.73; S, 4.56. Calc. for C49H24F18P2Pd2S2: C,
45.50; H, 1.87; S, 4.96%. IR (cmꢄ1): C6F5 and SC6HF4,
1H-NMR (d, ppm): CH2, 4.6 (t, JPꢀH
ꢁ
/
11 Hz),
SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4,
ꢄ
/
129.6 (m, Fo), ꢄ
Jom 22 Hz, JPtꢀF
164.2 (t, Jmp
19 Hz, Fp). 31P{1H}-NMR (d, ppm):
52.4 (s, JPtꢀP
2635 Hz). MS (m/z) FABꢃ: M,
(C6F5), 1303(4%); (2C6F5),
(2C6F5ꢃSC6HF4),
SC6HF4ꢃPt), 760(100%).
1470(7%); Mꢀ(dppmꢃSC6HF4ꢃ
(C6F5ꢃ2SC6HF4ꢃ4C6H5ꢃPt), 348(20%).
/
139.1 (m, Fm); C6F5, ꢄ
/
120.2 (d,
n(Cꢀ
/
F) 1230m, 1173m, 1057s, 998m; n(Cꢀ
/
S) 914vs;
n(X-sensitive) 786s, 777s; dppm, n(chelate) 542s. 1H-
NMR (d, ppm): CH2, 4.3 (t, JPꢀH 11 Hz), SC6HF4, 6.5
ꢁ
/
ꢁ
/
443 Hz, Fo), ꢄ166.2 (m, Fm),
/
ꢄ
/
ꢁ
ꢁ
/
ꢄ
/
/
(m). 19F-NMR (d, ppm): SC6HF4, ꢄ
/
129.3 (m, Fo),
116.1 (d, Jom 28 Hz, Fo),
162.8 (t, Jmp
19 Hz, Fp). 31P{1H}-
NMR (d, ppm): ꢄ
(C6F5ꢃSC6HF4), 945(2%); Mꢀ
779(20%); (2C6F5ꢃSC6HF4ꢃ
Mꢀ
FABꢄ: M, 1292(7%); Mꢀ
(dppmꢃ
C6F5), 454(17%); (SC6HF4ꢃ2C6F5ꢃ
Mꢀ
623(100%).
1470(3%);
1136(5%);
(2C6F5ꢃ
Mꢀ
/
Mꢀ
955(5%);
FABꢄ:
/
ꢄ
/
139.2 (m, Fm); C6F5, ꢄ
/
ꢁ
/
Mꢀ
/
/
Mꢀ
/
ꢄ
/
164.9 (m, Fm), ꢄ
/
ꢁ
/
/
/
M,
/
41.4 (s). MS (m/z) FABꢃ: Mꢀ
/
/
/
/
Pt), 709(100%); Mꢀ
/
/
/
(2C6F5ꢃ
Pd),
Pdꢃ
/
SC6HF4),
/
/
/
/
/
/
671(58%).
SC6HF4ꢃ
2C6H5),
/
/
/
/
2.3. Crystal structure determination of
[Ni(SC6HF4)2(dppe)] (1), [(dppe)Ni(m-
SC6HF4)2Pd(C6F5)2] (6) and [(dppe)Ni(m-
SC6F5)2Pd(C6F5)2]
/
/
/
2.2.2.8. Compound 13. Yield: 69%. Anal. Found: C,
42.05; H, 1.53; S, 4.07. Calc. for C49H24F18P2PdPtS2: C,
42.58; H, 1.75; S, 4.64%. IR (cmꢄ1): C6F5 and SC6HF4,
Crystal data, and data collection and refinement
parameters, are summarized in Table 1. Single crystals
(reddish parallelepipeds, in every case) were grown by
slow diffusion of diethyl ether into a diluted dichlor-
ometane solution of the respective compounds, at r.t. A
fragment was mounted on top of a glass fibre, in a drop
of HMP lithium grease, and rapidly cooled down to 200
K.
Heavy atom methods [15], were used to locate the
transition metal(s), sulfur and phosphorus atoms, while
subsequent cycles of full-matrix least-squares refinement
[16] and difference Fourier maps were used to locate the
remaining non-hydrogen atoms; all non-H atoms,
anisotropic. Hydrogen atoms were placed at geometri-
cally calculated positions, and their positional coordi-
nates were constrained (taking into account the
temperature) to ride on those of the corresponding
carbon atoms, with dependent isotropic displacement
parameters. Selected bond lengths and angles are given
n(Cꢀ
/
F) 1226s, 1170s, 1055vs,999s; n(Cꢀ
/
S) 915vs; n(X-
1
sensitive) 786s, 778s; dppm, n(chelate) 555vs. H-NMR
(d, ppm): CH2, 4.6 (t, JPꢀH 11 Hz), SC6HF4, 6.5 (m).
19F-NMR (d, ppm): SC6HF4, ꢄ
/
129.0 (m, Fo), ꢄ
26 Hz, Fo), ꢄ165.1 (m,
19 Hz, Fp). 31P{1H}-NMR (d,
2667 Hz). MS (m/z) FABꢃ:
SC6HF4), 1034(8%); Mꢀ(2C6F5ꢃSC6HF4),
867(27%); Mꢀ(2C6F5ꢃSC6HF4ꢃPd), 760(82%); Mꢀ
(2C6F5ꢃSC6HF4ꢃPt), 672(13%). M,
FABꢄ:
1381(5%); Mꢀ(C6F5), 1214(16%); Mꢀ(C6F5ꢃSC6HF4),
1032(7%); Mꢀ(SC6HF4ꢃ2C6F5ꢃ3C6H5), 635(100%);
Mꢀ(SC6HF4ꢃ2C6F5ꢃ3C6H5ꢃPd), 529(20%).
/
139.2
(m, Fm); C6F5, ꢄ
Fm), ꢄ162.8 (t, Jmp
ppm): ꢄ52.4 (s, JPtꢀP
Mꢀ(C6F5ꢃ
/116.6 (d, Jom
ꢁ
/
/
/
ꢁ
/
/
ꢁ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.2.2.9. Compound 14. Yield: 69%. Anal. Found: C,
41.97; H, 1.70; S, 4.61. Calc. for C49H24F18P2PdPtS2: C,
42.58; H, 1.75; S, 4.64%. IR (cmꢄ1): C6F5 and SC6HF4,
n(Cꢀ
/
F) 1249m, 1230m, 1173s, 1060vs, 1014m; n(Cꢀ
/
S)
in Tables 2ꢂ4; other crystallographic data are available
/
914s; n(X-sensitive) 800m, 791s; dppm, n(chelate) 542m.
1H-NMR (d, ppm, d6-acetone): CH2, 5.2 (t, JPꢀH 11
Hz), SC6HF4, 6.5 (m). 19F-NMR (d, ppm): SC6HF4,
as supplementary material.
ꢄ
/
129.8 (m, Fo), ꢄ
Jom 27 Hz, JPtꢀF
165.3 (t, Jmp
19 Hz, Fp). 31P{1H}-NMR (d, ppm):
32.5 (s). MS (m/z) FABꢃ: M, 1381(6%); Mꢀ
(C6F5),
1213(11%); Mꢀ(2C6F5), 1048(9%); Mꢀ(2C6F5ꢃSC6-
HF4), 865(21%); Mꢀ(2C6F5ꢃSC6HF4ꢃPt), 671(65%);
Mꢀ(2C6F5ꢃSC6HF4ꢃPd), 761(14%); Mꢀ(C6F5ꢃ
SC6HF4), 1034(23%); Mꢀ
(SC6HF4), 1199(3%). FABꢄ:
M, 1381(19%); Mꢀ(dppmꢃSC6HF4ꢃPd), 709(100%);
Mꢀ(C6F5ꢃ2SC6HF4ꢃ4C6H5ꢃPt), 349(18%).
/
139.8 (m, Fm); C6F5, ꢄ
/
117.6 (d,
3. Results and discussion
ꢁ
/
ꢁ
/
440 Hz, Fo), ꢄ166.6 (m, Fm),
/
ꢄ
/
ꢁ
/
3.1. Mononuclear complexes
ꢄ
/
/
/
/
/
Addition (2:1) of thallium p-tetrafluorobenzenethio-
late to a slurry of cis-[MCl2(LꢀL)] in acetone leads to
the formation of the corresponding bis(tetrafluorothio-
/
/
/
/
/
/
/
/
/
/
phenolato) complex.
/
/
/
/
/
/
/
cis[MCl2(LꢀL)]ꢃ2Tl(SC6HF4)
0 cis[M(SC6HF4)2(LꢀL)]ꢃ2TlCl¡
LꢀLꢁdppe; MꢁNi (1), Pd (2), Pt (3); Lꢀ
MꢁPd (4), Pt (5).
(1)
2.2.2.10. Compound 15. Yield: 69%. Anal. Found: C,
39.87; H, 1.67; S, 4.29. Calc. for C49H24F18P2Pt2S2: C,
40.01; H, 1.64; S, 4.36%. IR (cmꢄ1): C6F5 and SC6HF4,
/
/
/
/
Lꢁ
/
dppm;
/
n(Cꢀ
/
F) 1254m, 1228s, 1177s, 1059vs, 1000m; n(Cꢀ
/
S)
916vs; n(X-sensitive) 801s, 791s; dppm, n(chelate) 555vs.
The reaction being driven by the scarce solubility of
the thallium chloride, which forms as a very fine

´
102
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ107
/
Table 1
Crystal data and structure refinement for [Ni(SC6HF4)2(dppe)], [(dppe)Ni(m-SC6HF4)2Pd(C6F5)2] and [(dppe)Ni(m-SC6F5)2Pd(C6F5)2]
Formula
C38H26F8NiP2S2
819.36
Triclinic
C50H26F18NiP2PdS2
1259.88
C50H22F20NiP2PdS2
1295.86
Formula weight
Crystal system
Space group
Monoclinic
P21/c (number 14)
14.3715(11)
13.4324(9)
24.826(2)
Monoclinic
P21/n (number 14)
13.5461(14)
23.303(2)
¯
P1 (number 2)
/
˚
a (A)
10.082(2)
11.264(3)
16.936(4)
93.63(2)
˚
b (A)
˚
c (A)
15.3644(14)
90
a (8)
b (8)
g (8)
V (A )
Z
90
104.828(15)
109.845(14)
1724.8(8)
2
100.622(8)
90
4710.3(6)
98.716(11)
90
4794.1(8)
3
˚
4
1.777
4
1.795
Dcalc (g cmꢄ3
Crystal size (mm3)
m (mmꢄ1
Transm factors: max/min
Data collection instrument
)
1.578
0.27ꢅ0.27ꢅ0.19
0.849
0.57ꢅ0.27ꢅ0.23
1.047
0.57ꢅ0.48ꢅ0.46
1.037
)
0.992, 0.806
Stoe-Siemens AED2
0.703, 0.632
Stoe-Siemens AED2
1.000, 0.930
Stoe-Siemens AED2
˚
Radiation (A)
Moꢂ
200
v ꢂ
1.95ꢂ
6441
/
Ka, lꢁ0.71073
Moꢂ
200
v ꢂ
1.67ꢂ
9012
/
Ka, lꢁ0.71073
Moꢂ
200
v ꢂ
1.60ꢂ
9328
/
Ka, lꢁ0.71073
Temperature (K)
Scan method
/
u
/
u
/
u
u Collection range (8)
Measured reflections
/
25.00
/24.52
/25.51
Unique data [Rint]
Number of parameters refined
6062 [0.0383]
460
7837 [0.0110]
667
8934 [0.1083]
685
a
R1 [I ꢀ2s(I)], (number of data)
wR2 (all data)
0.0506 (3748)
0.0891
.0299 (6145)
0.0655
.0512 (6657)
0.1474
b
c
Weighting parameters: g1, g2
d
0.0272, 0.0000
0.991
0.0332, 1.2770
0.985
0.0739, 10.7980
1.062
Quality-of-fit (on F2)
Largest shift/estimated S.D., final cycle
ꢄ0.001
0.406, ꢄ0.347
ꢄ0.001
0.377, ꢄ0.439
ꢄ0.001
1.154, ꢄ1.630
ꢄ3
˚
Largest peak, hole (e A
)
a
R1ꢁajjFojꢄjFcjj/ajFoj.
wR2ꢁ[a[w(F2oꢄF2c)2/a w(Fo2)2]]0.5
.
b
c
wꢁ[s2(F2o)ꢃ(g1P)2ꢃg2P]ꢄ1; Pꢁ[max(Fo2; 0)ꢃ2F2c]/3.
Quality-of-fitꢁ[a[w(F2oꢄFc2)2/(NobservationsꢄNparameters)]0.5
d
.
The IR spectra of the solids show, along with other
typical absorptions of the polyfluorophenyl ring [17ꢂ19]
and those due to the neutral bidentate ligand, a strong
band in the 910ꢂ
915 cmꢄ1 region which, by comparison
with the homologous pentafluorothiophenolate com-
plexes [7], can be tentatively assigned to the n(CꢀS)
vibrations of the tetrafluorothiolato groups [19,20].
/
Table 2
˚
Selected bond lengths (A) and angles (8) for [Ni(SC6HF4)2(dppe)] (1)
/
Bond lengths
Ni1ꢀP1
Ni1ꢀP2
Ni1ꢀS1
Ni1ꢀS2
S1ꢀC31
S2ꢀC41
2.1714(14)
2.1817(14)
2.2041(14)
2.2182(15)
1.751(5)
/
Complexes 4 and 5 show a strong band at 538 or, 548
cmꢄ1, respectively, characteristic [21] of the dppm
ligand acting as a chelate.
1.762(4)
Bond angles
P1ꢀNi1ꢀP2
P1ꢀNi1ꢀS1
P2ꢀNi1ꢀS1
P1ꢀNi1ꢀS2
P2ꢀNi1ꢀS2
S1ꢀNi1ꢀS2
C31ꢀS1ꢀNi1
C41ꢀS2ꢀNi1
The 31P-NMR spectra of complexes 1ꢂ
5 show a single
/
85.78(5)
97.74(5)
signal (along with the expected platinum satellites in the
case of compounds 3 and 5) indicating that in solution
both phosphorus nuclei are equivalent. The negative
value (to low frequencies from 85% H3PO4, as the
reference) of the chemical shift in complexes 4 and 5
proves [21] the chelate character of the bis(diphenylpho-
sphino)methane ligand.
175.29(6)
161.10(5)
85.20(5)
92.31(6)
113.66(15)
113.09(15)
The 19F-NMR spectra of complexes 1ꢂ
125 to ꢄ135 ppm region, assignable to the ortho-
/
5 show (in the
ꢄ
/
/
precipitate that must be carefully filtered off. Evapora-
tion of the clear solution to dryness, and addition of
diethyl ether or hexane, affords the desired complex.
fluorine nuclei of the tetrafluorothiophenolato groups,
see ref. [22]) a multiplet, as expected from the coupling
to both meta-fluorine and the para proton nuclei. No

´
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
103
Table 3
Table 4
˚
˚
Selected bond lengths (A) and angles (8) for [(dppe)Ni(m-
SC6HF4)2Pd(C6F5)2] (6)
Selected bond lengths (A) and angles (8) for [(dppe)Ni(m-
SC6F5)2Pd(C6F5)2] (6)
Bond lengths
Bond lengths
NiꢀP1
NiꢀP2
NiꢀS2
2.1849(9)
2.1966(9)
2.2640(9)
2.2826(8)
2.015(3)
2.024(3)
2.3796(8)
2.3818(8)
1.762(3)
1.771(3)
NiꢀP2
NiꢀP1
NiꢀS1
2.1817(14)
2.1819(14)
2.2592(14)
2.2654(14)
2.007(5)
NiꢀS1
NiꢀS2
PdꢀC61
PdꢀC51
PdꢀS2
PdꢀS1
S1ꢀC31
S2ꢀC41
PdꢀC61
PdꢀC51
PdꢀS2
PdꢀS1
S1ꢀC31
S2ꢀC41
2.021(5)
2.3719(13)
2.3780(13)
1.749(6)
1.763(6)
Bond angles
P1ꢀNiꢀP2
P1ꢀNiꢀS2
P2ꢀNiꢀS2
P1ꢀNiꢀS1
P2ꢀNiꢀS1
S2ꢀNiꢀS1
C61ꢀPdꢀC51
C61ꢀPdꢀS2
C51ꢀPdꢀS2
C61ꢀPdꢀS1
C51ꢀPdꢀS1
S2ꢀPdꢀS1
C31ꢀS1ꢀNi
C31ꢀS1ꢀPd
NiꢀS1ꢀPd
C41ꢀS2ꢀNi
C41ꢀS2ꢀPd
NiꢀS2ꢀPd
Bond angles
P2ꢀNiꢀP1
P1ꢀNiꢀS1
P1ꢀNiꢀS1
P2ꢀNiꢀS2
P1ꢀNiꢀS2
S1ꢀNiꢀS2
C61ꢀPdꢀC51
C61ꢀPdꢀS2
C51ꢀPdꢀS2
C61ꢀPdꢀS1
C51ꢀPdꢀS1
S2ꢀPdꢀS1
C31ꢀS1ꢀNi
C31ꢀS1ꢀPd
NiꢀS1ꢀPd
C41ꢀS2ꢀNi
C41ꢀS2ꢀPd
NiꢀS2ꢀPd
85.28(3)
173.10(3)
98.64(3)
85.72(5)
171.60(6)
94.69(5)
92.16(5)
170.88(6)
88.71(5)
91.7(2)
88.56(3)
173.62(3)
87.65(3)
87.15(12)
93.62(8)
92.79(14)
174.12(14)
174.98(14)
92.24(14)
83.51(4)
114.0(2)
99.64(18)
93.76(5)
112.0(2)
101.65(18)
93.77(5)
177.83(9)
171.72(9)
96.18(9)
82.79(3)
110.68(11)
110.60(10)
90.65(3)
113.96(12)
100.36(10)
91.16(3)
smallest one. The five-membered NiP2C2 chelate ring is
puckered [25] (28% twist with axis through Ni1 and P1
and 72% envelope with flap at C1).
5
coupling to 31P or 195Pt is observed (i.e. JPꢀF and
4JPtꢀF
0).
All these data support a mononuclear nature for
complexes 1ꢂ5 and a cis configuration, as proposed in
Eq. (1).
$
/
The nickelꢂphosphorus distances (2.171(1) and
/
/
˚
2.182(1) A) are similar and comparable with those of
the homologous compound with perfluorobenzenethio-
˚
lato (2.182(3) and 2.193(3) A). On the other hand, the
NiꢀS bond distances in compound (1) (2.218(1) and
2.204(1) A) are close to those found for the pentafluor-
3.2. Molecular structure of [Ni(SC6HF4)2(dppe)]
/
˚
˚
obenzenethiolato complex (2.216(3) and 2.218(3) A).
Amongst the above described mononuclear com-
plexes which gave single crystals suitable for an X-ray
diffraction study, [Ni(SC6HF4)2(dppe)] (1) was chosen
(see Fig. 1 for structure and numbering scheme) since its
structure could be compared with that of the analogous
compound with pentafluorothiophenolate as a ligand,
which has already been established by Torrens et al. [23].
For the sake of comparison, the positional parameters
for this last compound have been retrieved from the
Cambridge Structural Database [24].
The sulfurꢂcarbon bonds in compound (1), (1.751(5)
/
˚
and 1.762(4) A) are not very different to those found for
the pentafluorothiophenolato complex (1.766(10) and
˚
1.761(10) A). This may appear in clear contrast with the
wavenumber of the IR band assigned to mainly the
n(Cipso
S) stretching [7,19,20]: 858 cmꢄ1 for the SC6F5
ꢀ
/
compound against 909 cmꢄ1 for the SC6HF4 complex
(1); however, as has already been stated [18,19,26], the
so called ‘X-sensitive’ vibration of C6F5-X groups is not
a ‘pure’ carbon-X stretching, but includes the contribu-
tions of other motions of the same symmetry species.
A striking difference between both homologous
compounds is the absence of interfacial interactions [5]
between the aromatic tetrafluorotiophenolato rings of
compound 1, which has been observed before in many
Coordination around the nickel centre in compound
(1) is distorted square-planar (the angles around Ni1
add to 361.08, and the mean deviation for the best plane
˚
defined by the Ni1, S1, S2, P1 and P2 atoms is 0.176 A).
The bonding angles vary between 85.20(5) and 97.74(6)8
although the widest angle is not that opposite to the P1ꢀ
/
NiꢀP2 which, due to the chelate bite, is necessarily the
/
pentafluorobenzenetiolato compounds [1ꢂ4]. For in-
/

´
104
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ107
/
Fig. 1. Molecular structure and numbering scheme for [Ni(SC6HF4)2(dppe)] (1); ellipsoids at 30% probability.
stance, in [Ni(SC6F5)2(dppe)], both rings are almost
parallel: they form an angle of only 4.98, they are set off
Thus, when a dichloromethane or acetone solution of
cis-[M(SC6HF4)2(LꢀL)] is treated with an equivalent
amount of cis-[M?(C6F5)2(THF)2], the two labile tetra-
hydrofurane groups are readily displaced and the
desired dinuclear compound is formed, according to
Eq. (2).
/
˚
[5] by 1.781 A and the mean distance between planes is
˚
just 3.226 A. In compound (1), one of the tetrafluor-
otiophenolato rings is not so parallel to one of the
phenylic rings of the diphosphine, with a dihedral angle
of 7.1(3)8, a distance between planes (calculated as the
mean of the separations of each C6-centroid to the
˚
opposite plane) of 3.322 A and the offset of the rings is
˚
0.924 A, while the polyfluorothiolate rings form an
cis[M(SC6HF4)2(LꢀL)]ꢃcis[M?(C6F5)2(THF)2]
0 [(LꢀL)M(mSC6HF4)2M?(C6F5)2]ꢃ2THF
(2)
angle of 82.00(13)8.
Lꢀ
Lꢁdppe, M?ꢁ
dppm, M?ꢁPd, Mꢁ
M?ꢁPt, MꢁPd (14), Pt (15).
For compounds 6ꢂ15, the solvent was evaporated and
/
Lꢁ
/
dppe, M?ꢁ
Pt, Mꢁ
Pd (12), Pt (13); Lꢀ
/
Pd, Mꢁ
Ni (9), Pd (10), Pt (11); Lꢀ
Lꢁdppm,
/
Ni (6), Pd (7), Pt (8); Lꢀ
/
/
/
/
/
Lꢁ
/
/
/
/
/
3.3. Binuclear complexes
/
/
/
The cis-geometry of the mononuclear complexes,
together with the ability of thiolato groups to act as
bridging ligands [27], make them especially adequate for
the synthesis of geminal homo- or heterobinuclear
compounds. Selection of the reactants permited the
isolation of two pairs of binuclear coordination position
isomers.
the residue was washed with diethyl ether and methanol.
The IR spectra of these binuclear complexes (besides
other absorptions, which arise from the tetrafluoroben-
zenethiolato and the pentafluorophenyl rings [17ꢂ
/
19])
show two bands in the 805ꢂ
/
760 cmꢄ1 region (‘X-
sensitive vibration’ [18,26]) indicative of a cis geometry
of the pentafluorophenyl groups, and a somewhat broad

´
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
105
peak around 910 cmꢄ1 assignable to the n(Cipso
vibrations of the thiolate moieties.
Amongst other bands due to the neutral ligands, a
ꢀ
/
S)
ppm, SC6HF4) were observed in the ortho-fluorine
region, the later pointing to an exchange process.
The meta fluorine nuclei can be assigned (ꢄ
/
139.8
strong one around 550 cmꢄ1, indicative [21] of chelating
ppm, SC6HF4; ꢄ166.6 ppm, C6F5), since the former
/
dppm, can be observed for compounds 12ꢂ
/
15.
signal shows some broadening while the latter multiplet
presents a residual coupling to 195Pt in the base of the
signal.
The 31P{1H}-NMR spectra in solution consist of a
single peak (flanked by platinum satellites in the case of
compounds 8, 11, 13, 15) the phosphorus nuclei being,
thus, magnetically equivalent. Again, the high field
position of the resonance (relative to 85% H3PO4) in
In the 31P{1H}-NMR spectrum, a broad signal was
observed at ꢄ
/
32.5 ppm, comfirming a dynamic process.
Hence, a variable temperature (ꢄ
/
85 to ꢃ
/
55 8C)
31P{1H}-NMR study was undertaken, to no avail since
always a more or less broad signal is observed, with no
splitting nor coalescence. We suppose that various
exchange processes coexist (e.g. restricted rotation
compounds 12ꢂ
bidentate dppm ligand.
Complexes 6ꢂ15 show, in the ortho-fluorine region,
two doublets: one in the ꢄ110 to ꢄ122 range (penta-
fluorophenyl) and another between ꢄ125 and ꢄ135
/15 proves [21] the chelating roˆle of the
/
/
/
/
/
around the Cꢀ
/
S bonds, along with interconversion
ppm (tetrafluorobenzenethiolate ligand) [22]; in the case
of compounds 8, 11, 13, 15, the doublet at higher
frequency is escorted by 195Pt satellites, as expected.
Due to the scarce solubility of compound 14 in
chloroform, its 19F-NMR spectrum was recorded using
hexadeuteroacetone as the solvent; at room tempera-
between the syn ꢂ
/
exo, syn ꢂendo and anti conformers
/
through inversion at the sulfur centres), as commonly
encountered [28] in doubly thiolato-bridged binuclear
compounds.
Such fluxional behavior has already been described [7]
for the homologous perfluorophenylthiolate complex in
hexadeuteroacetone solution, for which it was found to
be solvent dependent.
ture, a doublet with 195Pt satellites (dꢁ
/
ꢄ
/
117.6 ppm,
4JPtꢀF
ꢁ
/
440 Hz, C6F5) and a broad peak (dꢁ
/
ꢄ
/
129.8
Fig. 2. Molecular structure and numbering scheme for [(dppe)Ni(m-SC6HF4)2Pd(C6F5)2] (6); ellipsoids at 30% probability.

´
106
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ107
/
(Lꢀ
/
L)M(m-SC6HF4)2M?(C6F5)2ꢃ(C6HF4S)M?(C6F5)2;
/
the low tendency of bis(diphenylphosphine)methane to
act as a chelate ligand may be the reason why this
fragment is formed, since it is not observed when Lꢀ
/
L is
dppe.
Scheme 1.
3.5. Molecular structures of [(dppe)Ni(m-
SC6HF4)2Pd(C6F5)2] (6) and [(dppe)Ni(m-
SC6F5)2Pd(C6F5)2]
3.4. Mass spectroscopical results
Mass spectra in the FABꢃ, as well as in the FABꢄ
As expected, coordination around the nickel and
palladium centres in compound 6 (see Fig. 2) is
square-planar (the sum of the bond angles are 360.1
and 359.78, the mean deviations from the least-squares
techniques were recorded for the [(LꢀL)M(m-
/
SC6HF4)2M?(C6F5)2] complexes. Noteworthy general
features are as follows.
While in the FABꢃ spectra the L2M(SC6HF4) and
˚
planes are 0.0636 and 0.0592 A, respectively). The two
(LꢀL)M(SC6HF4)M? fragments are invariably present,
/
coordination planes form a dihedral angle of 30.32(5)8,
and the thiolato ligands adopt an anti comformation.
The chelate ring is puckered [25] (41% twist with axis
through P1 and C1, and 59% envelope with flap at C2).
in FABꢄ the most important peak is due to the
(C6HF4S)M?(C6F5)2 fragment (this agrees with the
formal charge distribution, positive on M and negative
on M?) (Scheme 1).
On formation of the double thiolato bridge, the
˚
nickelꢂphosphorus (2.1849(9) and 2.1966(9) A) and,
In those compounds containing dppm as the ancillary
ligand, a peak above the molecular mass is always
observed. It can be attributed as the addition fragment
/
most noteworthy, the nickelꢂ
/
sulfur (2.2640(9) and
˚
2.2826(8) A) distances increase only slightly.
Fig. 3. Molecular structure and numbering scheme for [(dppe)Ni(m-SC6F5)2Pd(C6F5)2]; ellipsoids at 30% probability.

´
M.A. Uson, J.M. Llanos / Journal of Organometallic Chemistry 663 (2002) 98ꢂ
/107
107
One of the tetrafluorothiophenolato rings exhibits an
interfacial interaction with one phenyl ring of the
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˜
˚
˚
off by 0.889 A, and the mean separation is 3.348 A.
In the homologous [(dppe)Ni(m-SC6F5)2Pd(C6F5)2]
the coordination around the nickel and palladium
centres is ca. square-planar (the sum of the bonding
angles are 361.3 and 360.28, the mean deviations are
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0.1479 and 0.0614 A, respectively). The dihedral angle
between the two coordination planes is 6.53(13)8, and
the thiolato ligands are in an anti comformation. Fig. 3
shows the numbering scheme and the structure.
The chelate NiP2C2 ring is puckered [25] (64% twist,
with axis through Ni and P1, and 36% envelope, with
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flap at C1).
The nickelꢂ
distances almost do not vary, and nickelꢂ
(2.2592(14) and 2.2654(14) A) bonds are only slightly
longer than those of the parent mononuclear compound
[23].
˚
phosphorus (2.1817(14) and 2.1819(14) A)
/
[9] M.E. Peach, Can. J. Chem. 46 (1968) 2699.
[10] G.R. van Hecke, W.D. Horrocks, Jr., Inorg. Chem. 5 (1966) 1968.
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/sulfur
˚
[13] R. Uso´n, J. Fornie´s, M. Toma´s, B. Menjo´n, Organometallics 4
(1985) 1912.
In this compound, both thiolato rings show interfacial
interactions, each to one phenyl ring of the diphosphine.
[14] M.A. Uso´n, J. Chem. Educ. 66 (1990) 412.
[15] G.M. Sheldrick, SHELXTL PLUS, release 5.05, for Digital Alpha/
VMS, Siemens Analytical X-Ray Instruments, Madison, WI,
1996.
So, ring C31ꢀ
/
C36 interacts with C11bꢀ
/
C16b (the angle
is 5.93(28)8, the offset 0.972 and the mean distance is
˚
3.264 A) while ring C41ꢀ
/
C46 interacts with C21bꢀ
/
C26b
[16] G.M. Sheldrick, SHELXL-97: A Program for Crystal Structure
(angle 6.11(27)8, offset 1.140 and mean distance between
Refinement, Universitat Gottingen, BRD, 1997.
¨ ¨
[17] G.B. Deacon, J.H.S. Green, Spectrochim. Acta Part A 24 (1968)
1125.
˚
planes of 3.286 A).
The structure of a related compound with double
thiophenol bridges between palladium and nickel,
[(dppe)Pd(m-SC6H5)2Ni(C6F5)2], has been recently pub-
lished [29].
[18] D.A. Long, D. Steele, Spectrochim. Acta 19 (1963) 1955.
[19] W. Beck, K.H. Stetter, S. Tadros, K.E. Schwarzhans, Chem. Ber.
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[21] J. Fornie´s, R. Navarro, E.P. Urriolabeitia, J. Organomet. Chem.
390 (1990) 257.
4. Supplementary material
[22] R. Uso´n, J. Fornie´s, M.A. Uso´n, J.A. Apaolaza, Inorg. Chim.
Acta 187 (1991) 175.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
[23] R.M. Catala´, M.E. Colsa, D. Cruz-Garritz, H. Torrens, J.L.
Brianso, J.E. Piniella, G. Germain, Transition Met. Chem. 12
(1987) 197 (refcode NACLUY).
Data Centre, CCDC nos. 185711ꢂ185713. Copies of this
/
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
[24] Cambridge Structural Database, Cambridge Crystallographic
Data Centre, University Chemical Laboratory, Cambridge,
October 2001 Release for VMS.
UK (Fax: ꢃ44-1233-336033; e-mail: deposit@ccdc.ca-
/
m.ac.uk or www: http://www.ccdc.cam.ac.uk).
[25] R.O. Gould, P. Taylor, M.C. Thorpe, PUCKER, University of
Edinburgh, UK, 1995.
[26] R. Uso´n, J. Fornie´s, F. Mart´ınez, M. Toma´s, J. Chem. Soc.
Dalton Trans. (1980) 888.
Acknowledgements
[27] P.J. Blower, J.R. Dilworth, Coord. Chem. Rev. 76 (1987) 121.
[28] E.W. Abel, S.K. Bhargava, K.G. Orrell, Prog. Inorg. Chem. 32
(1984) 1.
This work was supported by the Direccio´n General de
Ensenanza Superior e Investigacio´n Cient´ıfica (grant
˜
[29] G. Sa´nchez, F. Momblona, M. Sa´nchez, J. Pe´rez, G. Lo´pez, J.
Casabo´, E. Molins, C. Miravitlles, Eur. J. Inorg. Chem. (1998)
1199; refcode PUHKEI, retrieved from [24].
PB98-1595-C02-01). J.M.L. thanks the European Scien-
tific Council for the award of a scholarship/contract.