Hz], 229.3 [d, 1J(PPt) 1708 Hz]. 13C{1H}: d 138.6 [t, CH, 2J(PtC) 85 Hz],
131.4 (s, 2CH), 129.8 (s, C), 129.8 (s, CH), 129.7 [dd, CH, 2J(trans-PC)
100.6, 2J(cis-PC) 8.6 Hz], 125.3 (s, C), 121.7 (s, CH).
‡ [Pt(C,S-SC8H6)(dppe)] 2. Anal. Calc. for C34H30P2PtS·CH2Cl2: C, 51.7;
H, 4.0. Found: C, 52.2; H, 3.8%. NMR (CDCl3), 1H d 2.25–2.6 (m, CH2, 4
H), 7.0–8.0 (m, CH + Ar, 26 H). 31P: d 41.5 [d, 1J(PtP) 1743 Hz, 2J(PP) 6
Hz], 46.3 [d, 1J(PtP) 3122 Hz]. FABMS: m/z 728.
C(12)
C(13)
C(20)
C(19)
C(17)
Pt
C(11)
C(21)
C(18)
C(34)
C(10)
C(14)
C(15)
Crystal data for C35H32Cl2P2PtS: M
= 812.60, crystallised from
C(7)
CH2Cl2–hexane as yellow blocks and containing one molecule of CH2Cl2;
crystal dimensions 0.48 3 0.38 3 0.27 mm. Monoclinic, space group P21/n
C(16)
C(6)
(a non-standard setting of P21/c,C5
,
no. 14),
a
=
9.5594(7),
C(1)
2h
P(1)
b = 19.5003(14), c = 17.4993(12) Å, b = 91.683(2), U = 3260.7(4) Å3,
Z = 4, Dc = 1.655 Mg m23, Mo-Ka radiation (l = 0.710 73 Å), m(Mo-
Ka) = 4.653 mm21, F(000) = 1600.
C(2)
C(5)
C(8)
Refinement converged at a final R = 0.0318 (wR2 = 0.0863, for all 5728
unique data, 372 parameters, mean and maximum d/s 0.000, 0.000), with
allowance for the thermal anisotropy of all non-hydrogen atoms. Minimum
and maximum final electron density 21.087 and 1.308 e A23
C(3)
C(9)
C(4)
.
P(2)
S(1)
§ [Pt(C,S-SC8H8)(dppe)], 3. Anal. Calc. for C34H32P2PtS·0.5CHCl3: C,
52.5; H, 4.2; Found: C, 53.1; H, 4.4%. NMR spectra in CDCl3, 1H: d 1.1–1.4
(m, 3 H, CH3), 1.9–2.7 (m, 4 H, CH2), 3.1–3.5 (m, 1 H, CH), 6.7 (t, 1 H, Ar),
6.8 (t, 1 H, Ar), 6.9 (d, 1 H, Ar), 7.4–8.0 (m, 21 H, Ar). 31P: d 43.0 [1J(PtP)
1594, 2J(PP) 4 Hz], 45.9 [1J(PtP) 3190 Hz]. FABMS: m/z 730.
C(22)
C(28)
C(33)
C(32)
C(23)
C(27)
C(29)
C(24)
Crystal data for 3: C34H32P2PtS; M = 729.69, crystallised from CH2Cl2–
hexane as yellow blocks; crystal dimensions 0.43 3 0.26 3 0.12 mm.
Monoclinic, space group P21/c (C52h, No. 14), a = 9.266(4), b = 15.142(7),
c = 21.303(9) Å, b = 98.51(3), U = 2956(2) Å3, Z = 4, Dc = 1.640 Mg
C(26)
C(31)
C(30)
C(25)
Fig. 2 The molecular structure determined for 3. Bond lengths (Å) and
angles (°): Pt–P(1) 2.232(4), Pt–P(2) 2.313(4), Pt–S 2.328(4), Pt–C(1)
2.202(14), Pt–C(34) 3.05 Å; C(1)–Pt–P(1) 93.3(4), P(1)–Pt–P(2) 85.49(13),
C(1)–Pt–S, 82.7(4), P(2)–Pt–S 98.60(13)°.
m23, Mo-Ka radiation (l = 0.710 73 Å), m(Mo-Ka) = 4.948 mm21
F(000) = 1440.
,
Refinement converged at a final R = 0.0665 (wR2 = 0.1506, for all 5188
unique data 344 parameters, mean and maximum d/s 0.000, 0.000), with
allowance for the thermal anisotropy of all non-hydrogen atoms. Minimum
and maximum final electron density 20.892 and 1.150 e A23. CCDC
182/670.
Me
Ph2P
Ph2P
H2
CH
Ph2P
Pt
Pt
(CH2)2
(CH2)2
1 H. Topsoe, B. S. Clausen and F. Massoth, Hydrotreating Catalysis,
Springer, Berlin, p. 114; A. N. Startsev, Catal. Rev. Sci. Eng., 1995, 37,
353; B. C. Weygand and C. Friend, Chem. Rev., 1992, 92, 491;
C. M. Friend and D. A. Chen, Polyhedron, 1997, 16, 3165; B. Delmon,
Catal. Lett., 1993, 1–2, 1; O. Weisser and S. Landa, Sulphide Catalysts,
their Properties and Applications, Pergamon, Oxford, 1973.
2 J. P. van den Berg, J. P. Lucien, G. Germaine and G. L. B. Thielemans,
Fuel Process. Technol., 1993, 35, 119; B. H. Cooper, A. Stanislaus and
P. N. Hannerup, Hydrocarbon Process., 1993, 83; I. E. Maxwell,
J. E. Naber and K. P. de Jong, Appl. Catal., A: Gen., 1994, 113, 153;
S. Mignard, N. Marchal and S. Kasztelan, Bull. Soc. Chim. Belg., 1995,
104, 259; M. Sugioka, F. Sado, Y. Matsumoto and N. Maesaki, Catal.
Today, 1996, 29, 255.
3 J. J. Garcia, B. E. Mann, H. Adams, N. A. Bailey and P. M. Maitlis,
J. Am. Chem. Soc., 1995, 117, 2179; see also: J. J. Garcia and
P. M. Maitlis, J. Am. Chem. Soc., 1993, 115, 12200.
4 J. J. Garcia, A. Arevalo, V. Montiel, F. Del Rio, B. Quiroz, H. Adams
and P. M. Maitlis, Organometallics, 1997, 16, 3216.
5 J. J. Garcia, A. Arevalo, S. Capella, A. Chehata, M. Hernandez,
V. Montiel, G. Picazo, F. Del Rio, R. Toscano, H. Adams and
P. M. Maitlis, Polyhedron, 1997, 16, 3185.
6 R. J. Angelici, Polyhedron, 1997, 16, 3073 and following articles in
Polyhedron Symposium in Print on Hydrotreating; see also: C.
Bianchini and A. Meli, J. Chem. Soc., Dalton Trans., 1996, 801.
7 C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, P. Frediani, V. Herrera
and R. A. Sanchez-Delgado, J. Am. Chem. Soc., 1993, 115, 7505;
C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, S. Moneti, V. Herrera and
R. A. Sanchez-Delgado, J. Am. Chem. Soc., 1994, 116, 4370;
C. Bianchini, A. Meli, V. Patinec, V. Sernau and F. Vizza, J. Am. Chem.
Soc., 1997, 119, 4945.
8 V. Herrera, A. Fuentes, M. Rosales, R. A. Sanchez-Delgado, C. Bian-
chini, A. Meli and F. Vizza, Organometallics, 1997, 16, 2465.
9 D. A. Vicic and W. D. Jones, Organometallics, 1997, 16, 1912.
10 C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, P. Frediani, V. Herrera
and R. A. Sanchez-Delgado, J. Am. Chem. Soc., 1993, 115, 2731.
11 G. M. Sheldrick, SHELXL93, An integrated system for solving and
refining crystal structures from diffraction data, University of
Gottingen, Germany 1993.
Pt
H
(CH2)2
S
S
S
Ph2P
Ph2P
Ph2P
2
A
3
Scheme 1
2-ethylthiophenol, while the six-membered thiaplatinacycles
[Pt{C,S-(CHNCHC6H4S)}(PEt3)2] and 2 gave 2-vinylthio-
phenol.4
One attractive mechanism by which the reaction 2 ? 3 can
3
occur is via a s-S bonded p-alkene (h ) intermediate (A), as
shown in Scheme 1. Such species have been previously invoked
in the reactions of various thiophenes with metal hydrides; a
related iridium complex derived from thiophene itself has been
3
isolated
and
characterised
as
[(triphos)Ir(h -
S(Me)CHNCHCHNCH2)]+ [triphos = MeC(CH2PPh2)3], and
this shows equivalent bonding of the irdidium to both the CH
[2.19(3) Å] and to the CH2 [2.12(3) Å].10 That complex 3 does
not have a type A structure is shown by the Pt···Me distance
[Pt···C(34)] of 3.05 Å, which is well outside bonding; by
contrast the distance Pt–C(1) is 2.202(14) Å.
Complex 3 can be hydrodesulfurised to ethylbenzene (ca.
80%) with LiAlH4 (thf, 20 °C); this demonstrates a new HDS
pathway, BT ? 2 ? 3 ? PhEt.
We thank the EPSRC, the Royal Society, EERO, the
European Community (Contract CL1*CT94-0062) and CON-
ACYT for support and Professor W. Clegg for collecting the
data for complex 2.
Footnotes and References
* E-mail: P.Maitlis@Sheffield.ac.uk
† [Pt(C,S-SC8H6)(PMe3)2] 1. Anal. Calc. for C14H24P2PtS: C, 34.9; H, 5.0;
S, 6.65. Found: C, 35.0; H, 4.95; S, 6.7%. NMR (CDCl3): 1H: d 1.2–2.0 (m,
18 H, CH3), 7.0–7.1 (m, 1 H, CH), 7.1–7.2 (m, 1 H, CH), 7.2–7.4 (m, 2 H,
CH), 7.4–7.6 (m, 1 H, CH), 7.9 (m, 1 H, CH). 31P: d 222.6 [d, 1J(PPt) 3065
Received in Cambridge, UK, 15th September 1997; 7/06707K
62
Chem. Commun., 1998