Heterodi- [MAg, MAu (M = Pd, Pt)], Tri- [PdAg(2), PtAg(2), PtAu(2), Pt(2)M (M = Ni, Pt, Cd, Hg)], and Tetranuclear (Pt(2)Ag(2), Pt(2)Au(2)) 1,1-ethylenedithiolato complexes.
The reactions of [M(PPh(3))(2)[S(2)C=C[C(O)Me](2)]] [M = Pd (1a), Pt (1b)] with AgClO(4) and PPh(3) or with [Au(PPh(3))(OCMe(2))]ClO(4) afford heterodinuclear [[M(PPh(3))(2)][M'(PPh(3))][S(2)C=C[C(O)Me](2)]]ClO(4) [M = Pd, M' = Ag (2a), M = Pt, M' = Ag (2b), Au (4)] or trinuclear [[M(PPh(3))(2)][M'(PPh(3))](2)[S(2)C=C[C(O)Me](2)]](ClO(4))(2) [M = Pd, M' = Ag (3a), M = Pt, M' = Ag (3b), Au (5)] 1,1-ethylenedithiolato complexes, depending on the molar ratio of the reagents. We have recently reported that, in the absence of added PPh(3), the reactions of [Pt[S(2)C=C[C(O)Me](2)]L(2)] [L = PPh(3) (1b), L(2) = 1,5-cyclooctadiene (cod) (1c)] with AgClO(4) produce the heterotetranuclear derivatives [[PtL(2)](2)Ag(2)[S(2)C=C[C(O)Me](2)](2)]](ClO(4))(2) [L = PPh(3) (6a), L(2) = cod (6b)], which have been used now as efficient transmetallating agents toward gold, platinum, mercury, nickel, copper, or cadmium metal centers to give new types of 1,1-ethylenedithiolato complexes: [[Pt(PPh(3))(2)](2)Au(2)[S(2)C=C[C(O)Me](2)](2)](ClO(4))(2) (7), [(PtL(2))(2)M[S(2)C=C[C(O)Me](2)](2)](ClO(4))(2) [L(2) = cod, M = Pt (8), L = PPh(3), M = Hg (9)], [[Pt(PPh(3))(2)](2)[S(2)C=C[C(Me)=O](2)](2)Ni](ClO(4))(2) (10), and [[Pt(PPh(3))(2)](2)[S(2)C=C[C(Me)=O](2)](2)[M(OClO(3))(2)]] [M = Cu (11), [C(O)Me](2)] moieties but, whereas in 7 they bridge two gold(I) centers through the sulfur atoms, in 11 they chelate the copper(II) center through the oxygen atoms. The last one is the first example of such a coordination mode for the 2,2-diacetyl-1,1-ethylenedithiolato ligand.
Vicente
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J
Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Spain. jvs@fcu.um.es
Chicote
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Huertas
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Jones
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Fischer
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