Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu 4 ] 2 [{Pt(C 6 F 5 ) 2 (μ-SH)} 2 ], [Pt(C 6 F 5 ) 2 (PPh 3 ){S(H)AgPPh 3 }], and [Pt(C 6 F 5 ) 2 (PPh 3 ){S(AuPPh 3 ) 2 }] Jose ´ Ruiz,* Venancio Rodrı ´guez, Consuelo Vicente, Jose ´ M. Martı ´, and Gregorio Lo ´ pez Departamento de Quı ´mica Inorga ´nica, Universidad de Murcia, 30071-Murcia, Spain Jose ´ Pe ´ rez Departamento de Ingenierı ´a Minera, Geolo ´gica y Cartogra ´fica. A Ä rea de Quı ´mica Inorga ´nica, Universidad Polite ´cnica de Cartagena, 30203, Cartagena, Spain ReceiVed December 6, 2000 The reactions of the hydroxo complexes [M 2 R 4 (µ-OH) 2 ] 2- (M ) Pd, R ) C 6 F 5 ,C 6 Cl 5 ;M ) Pt, R ) C 6 F 5 ), [{PdR(PPh 3 )(µ-OH)} 2 ] (R ) C 6 F 5 ,C 6 Cl 5 ), and [{Pt(C 6 F 5 ) 2 } 2 (µ-OH)(µ-pz)] 2- (pz ) pyrazolate) with H 2 S yield the corresponding hydrosulfido complexes [M 2 (C 6 F 5 ) 4 (µ-SH) 2 ] 2- ,[{PdR(PPh 3 )(µ-SH)} 2 ], and [{Pt(C 6 F 5 ) 2 } 2 (µ- SH)(µ-pz)] 2- , respectively. The monomeric hydrosulfido complexes [M(C 6 F 5 ) 2 (SH)(PPh 3 )] - (M ) Pd, Pt) have been prepared by reactions of the corresponding binuclear hydrosulfido complexes [M 2 (C 6 F 5 ) 4 (µ-SH) 2 ] 2- with PPh 3 in the molar ratio 1:2, and they can be used as metalloligands toward Ag(PPh 3 ) + to form the heterodinuclear complex [(C 6 F 5 ) 2 (PPh 3 ){S(H)AgPPh 3 }], and toward Au(PPh 3 ) + yielding the heterotrinuclear complexes [M(C 6 F 5 ) 2 - (PPh 3 ){S(AuPPh 3 ) 2 }]. The crystal structures of [NBu 4 ] 2 [{Pt(C 6 F 5 ) 2 (µ-SH)} 2 ], [Pt(C 6 F 5 ) 2 (PPh 3 ){S(H)AgPPh 3 }], and [Pt(C 6 F 5 ) 2 (PPh 3 ){S(AuPPh 3 ) 2 }] have been established by X-ray diffraction and show no short metal-metal interactions between the metallic centers. Introduction There is much current interest in the chemistry of transition metal hydrosulfido complexes, mainly because these are useful in understanding many catalytic processes, such as hydrogena- tion and hydrodesulfuration. 1,2 However, these species are still quite rare, and hydrosulfido palladium or platinum complexes are very poorly represented. Only some terminal hydrosulfido compounds of the types [ML 2 (SH) 2 ] (M ) Pd or Pt; L 2 ) 2 PPh 3 , 2 PEt 3 ,2P i Bu 3 , or diphos), 3-5 [PtH(SH)L 2 ] (L 2 ) 2 PPh 3 , 2 PEt 3 ), 6,7 [PtH(SH)(triphos)], 8 or [PtR(SH)(dcpe)] (dcpe ) Cy 2 - PC 2 H 4 PCy 2 ,R ) Me, Ph, CH 2 tBu) 9 have been reported and, to the best of our knowledge, no examples of bridging hydrosulfido palladium or platinum are known so far. A tetranuclear palladium cluster with sulfide ligands, [{Pd(η 3 -C 4 H 7 )} 4 S 2 ], synthesized from the reaction of [Pd(η 3 -C 4 H 7 ) 2 ] and H 2 S, 10 has been shown to serve as a homogeneous catalyst. 11 The µ-hydroxo complexes of palladium and platinum of the types [M 2 R 4 (µ-OH) 2 ] 2- (M ) Pd, R ) C 6 F 5 ,C 6 Cl 5 ;M ) Pt, R ) C 6 F 5 ), 12,13 [{PdR(PPh 3 )(µ-OH)} 2 ] (R ) C 6 F 5 ,C 6 Cl 5 ;L ) PPh 3 ), 14 and [{Pt(C 6 F 5 ) 2 } 2 (µ-OH)(µ-pz)] 2- (pz ) pyrazolate) 15 have been shown to be excellent precursors in synthetic work. 17-19 We report now their reactions with H 2 S gas to give the first bridging hydrosulfido palladium and platinum com- plexes. The mononuclear hydrosulfido complexes [M(C 6 F 5 ) 2 (SH)- (PPh 3 )] - (M ) Pd, Pt), prepared from the corresponding dimers by addition of PPh 3 in the molar ratio 1:2, can be used as metalloligands toward M′(PPh 3 ) + (M′ ) Ag or Au), yielding heterobinuclear or heterotrinuclear complexes. In the hetero- trinuclear complexes [M(C 6 F 5 ) 2 (PPh 3 ){S(AuPPh 3 ) 2 }], it is pos- sible to envisage the isolobal analogy existing between the hydrogen atom and the AuPR 3 fragment. Some of these * To whom correspondence should be addressed. E-mail: jruiz@um.es. (1) Angelici, R. J. Acc. Chem. Res. 1988, 21, 387, and references therein. (2) Rakowski-Dubois, M. Chem. ReV. 1989, 89, 2, and references therein. (3) Schmidt, M.; Hoffmann, G. G.; Ho ¨ller, R. Inorg. Chim. Acta 1979, 32, L19. (4) Shaver, A.; Lai, R. D.; Bird, P.; Wickramsasinghe, W. Can. J. Chem. 1985, 63, 2555. (5) Ghillardi, C. A.; Midollini, S.; Nazzi, F.; Orlandini, A. Transition Met. Chem. 1983, 8, 73. (6) Ugo, R.; La Monica, G.; Cenini, S.; Segre, A.; Conti, F. J. Chem. Soc. A 1971, 522. (7) Garcı ´a, J. J.; Maitlis, P. M. J. Am. Chem. Soc. 1993, 115, 12200. (8) Cecconi, F.; Innocenti, P.; Midollini, S.; Moneti, S.; Vacca, A.; Ramirez, J. A. J. Chem. Soc., Dalton Trans. 1991, 1129. (9) Morton, M. S.; Lachicotte, R. J.; Vicic, D. A.; Jones, W. D. Organometallics 1999, 18, 227. (10) Bogdanovic, B.; Gottsch, P.; Rubach, M. Z. Naturforsch. B 1983, 38, 599. (11) Bogdanovic, B.; Gottsch, P.; Rubach, M. J. Mol. Catal. 1981, 11, 135. (12) Lo ´pez, G.; Ruiz, J.; Garcı ´a, G.; Vicente, C.; Casabo ´, J.; Molins, E.; Miravitlles, C. Inorg. Chem. 1991, 30, 2605. (13) Lo ´pez, G.; Ruiz, J.; Garcı ´a, G.; Martı ´, J. M.; Sa ´nchez, G.; Garcı ´a, J. J. Organomet. Chem. 1991, 412, 435. (14) Lo ´pez, G.; Ruiz, J.; Garcı ´a, G.; Vicente, C.; Martı ´, J. M.; Hermoso, J. A.; Vegas, A.; Martı ´nez-Ripoll, M. J. Chem. Soc., Dalton Trans. 1992, 53. (15) Ruiz, J.; C. Vicente, C.; Martı ´, J. M.; Cutillas, N., Garcı ´a, G.; Lo ´pez, G. J. Organomet. Chem. 1993, 460, 241. (16) Lo ´pez, G.; Ruiz, J.; Garcı ´a, G.; Vicente, C.; Rodrı ´guez, V.; Sa ´nchez, G.; Hermoso, J. A.; Martı ´nez-Ripoll, M. J. Chem. Soc., Dalton Trans. 1992, 1681. (17) Ruiz, J.; M. T. Martı ´nez; Vicente, C.; Garcı ´a, G.; Lo ´ pez, G.; Chaloner, P. A.; Hitchcock, P. B. Organometallics 1993, 12, 1594. (18) Ruiz, J.; Rodrı ´guez, V.; Lo ´pez, G.; Chaloner, P. A.; Hitchcock, P. B. Organometallics 1996, 15, 1662. (19) Ruiz, J.; Rodrı ´guez, V.; Lo ´ pez, G.; Casabo ´ , J.; Molins, E.; Miravitlles, C. Organometallics 1999, 18, 1177. 5354 Inorg. Chem. 2001, 40, 5354-5360 10.1021/ic0013633 CCC: $20.00 © 2001 American Chemical Society Published on Web 09/06/2001