Spivak Greg J., Vittal Jagadese J., Puddephatt Richard J.
Department of Chemistry, University of Western Ontario, London, Canada N6A 5B7.
Inorg Chem. 1998 Oct 19;37(21):5474-5481. doi: 10.1021/ic980555j.
The 84-electron hexaplatinum cluster complex [Pt(6)(&mgr;-CO)(6)(&mgr;-dppm)(3)], 1, dppm = Ph(2)PCH(2)PPh(2), reacts in a 1:2 molar ratio with either 0-electron metalloligands LM(+) (L = Ph(3)P, M = Cu, Ag, Au; L = iPr(3)P, M = Au) or InX(3) (X = Cl, Br) or 2-electron metalloligands Tl(+) and Hg to give the corresponding 84-electron clusters Pt(6)(&mgr;(3)-ML)(2)(&mgr;-CO)(6)(&mgr;-dppm)(3) or [Pt(6)(&mgr;(3)-InX(3))(2)(&mgr;-CO)(6)(&mgr;-dppm)(3)] or 88-electron clusters Pt(6)(&mgr;(3)-Tl)(2)(&mgr;-CO)(6)(&mgr;-dppm)(3) and [Pt(6)(&mgr;(3)-Hg)(2)(&mgr;-CO)(6)(&mgr;-dppm)(3)], respectively. The mercury cluster is oxidized by CH(2)I(2) to give the known 86-electron cluster [Pt(6)(&mgr;(3)-HgI)(2)(&mgr;-CO)(6)(&mgr;-dppm)(3)]. Reaction of 1 with Ir(CO)(4) occurs in a 1:1 ratio only to give the 98-electron anionic cluster Pt(6){&mgr;(3)-Ir(CO)(2)}(&mgr;-CO)(6)(&mgr;-dppm)(3), which reacts with Ph(3)PAu to give [Pt(6){&mgr;(3)-Ir(CO)(2)}(&mgr;(3)-AuPPh(3))(&mgr;-CO)(6)(&mgr;-dppm)(3)]. The new cluster complexes are characterized by NMR and IR spectroscopies, and Pt(6)(&mgr;(3)-AuPiPr(3))(2)(&mgr;-CO)(6)(&mgr;-dppm)(3) is also characterizedby an X-ray structure determination.
84电子的六铂簇配合物[Pt(6)(μ-CO)(6)(μ-dppm)(3)]（1），dppm = Ph(2)PCH(2)PPh(2)，与0电子金属配体LM⁺（L = Ph(3)P，M = Cu、Ag、Au；L = iPr(3)P，M = Au）或InX(3)（X = Cl、Br）或2电子金属配体Tl⁺和Hg按1:2的摩尔比反应，分别生成相应的84电子簇[Pt(6)(μ(3)-ML)(2)(μ-CO)(6)(μ-dppm)(3)]²⁺或[Pt(6)(μ(3)-InX(3))(2)(μ-CO)(6)(μ-dppm)(3)]或88电子簇[Pt(6)(μ(3)-Tl)(2)(μ-CO)(6)(μ-dppm)(3)]²⁺和[Pt(6)(μ(3)-Hg)(2)(μ-CO)(6)(μ-dppm)(3)]。汞簇被CH(2)I(2)氧化，生成已知的86电子簇[Pt(6)(μ(3)-HgI)(2)(μ-CO)(6)(μ-dppm)(3)]。1与[Ir(CO)(4)]⁻的反应仅按1:1的比例进行，生成98电子的阴离子簇[Pt(6){μ(3)-Ir(CO)(2)}(μ-CO)(6)(μ-dppm)(3)]⁻，它与[Ph(3)PAu]⁺反应生成[Pt(6){μ(3)-Ir(CO)(2)}(μ(3)-AuPPh(3))(μ-CO)(6)(μ-dppm)(3)]。这些新的簇配合物通过核磁共振和红外光谱进行表征，[Pt(6)(μ(3)-AuPiPr(3))(2)(μ-CO)(6)(μ-dppm)(3)]²⁺还通过X射线晶体结构测定进行了表征。
