The dinuclear head-to-tail complexes [M(2)(PPh(2)CH(2)SPh)(2)](2+) (M = Cu (1), Ag (2a, 2b), Au (4)) are obtained either by reaction of [Cu(CH(3)CN)(4)]CF(3)SO(3), AgClO(4), AgCF(3)SO(3), with equimolecular amounts of PPh(2)CH(2)SPh or of [AuCl(PPh(2)CH(2)SPh)] (3), prepared by reaction of [AuCl(tht)] and PPh(2)CH(2)SPh, with AgCF(3)SO(3). The crystal structures of complexes 2a and 4 have been established by X-ray diffraction studies. Ab initio HF/II and MP2/II calculations have been performed on the [M(2)(H(2)PCH(2)SH)(2)](2+) model, indicating that metallophilic attraction is indeed present for all the coinage metals as a correlation effect and is strengthened in the case of gold by relativistic effects. Since experimental and theoretically predicted geometries are in close agreement, we assume that our calculations are accurate enough to obtain valid conclusions.
Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.
The monohapto neutral 2-(diphenylphosphino)aniline (PNH 2 ) complexes [Au(C 6 F 5 ) 2 X(PNH 2 )] (X ) C 6 F 5 (1), Cl (2)) have been obtained from [Au(C 6 F 5 ) 3 (tht)] or [Au(C 6 F 5 ) 2 (µ-Cl)] 2 and PNH 2 , and the cationic [Au(C 6 F 5 ) 2 -(PNH 2 )]ClO 4 (3) has been similarly prepared from [Au(C 6 F 5 ) 2 (OEt 2 ) 2 ]ClO 4 and PNH 2 or from 2 and AgClO 4 . The neutral amido complex [Au(C 6 F 5 ) 2 (PNH)] ( 4) can be obtained by deprotonation of 3 with PPN(acac) (acac ) acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO 3 )(PPh 3 )] or [Au(OClO 3 )(PPh 3 )] to give the dinuclear species [Au(C 6 F 5 ) 2 {PNH(MPPh 3 )}]ClO 4 (M ) Ag ( 5), Au ( 6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh 3 )]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C 6 F 5 ) 2 {PN(AuPPh 3 ) 2 }]ClO 4 (7) is obtained. The crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)-Au(III) interaction.
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