Structural/bonding insights from new geometrical varieties of two Pt-Au carbonyl/phosphine clusters, [Pt3(AuPPh3)5(mu2-CO)2L3]+ (L3 = (CO)2PPh3) and [(mu6-Au){Pt3(mu2-CO)3L4}2]+ (L = PMe3) |
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Authors: | de Silva Namal Laufenberg Jeffrey W Dahl Lawrence F |
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Institution: | Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA. |
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Abstract: | Structural/bonding considerations of two new Pt-Au clusters, Pt3(AuPPh3)5(mu2-CO)2(CO)2PPh3]+ (1) and (mu6-Au){Pt3(mu2-CO)3(PMe3)4}2]+ (2) isolated (as chloride salts), revealed: (i) that the heretofore unknown 20-electron Pt-centered Pt2Au5 icosahedral cage fragment (five missing vertices) of is best viewed as a 44-electron triangular Pt3 adduct of a nearly planar 39-electron Pt3(mu2-CO)2L3]+ (L3 = (CO)2PPh3) and five one-electron donating AuPPh3 ligands; and (ii) that the geometrically distorted trimethylphosphine "full" Pt3AuPt3 sandwich of is the first example of two nucleophilic 44-electron triangular Pt3(mu2-CO)3L4 (3 : 3 : 4) units (L = PMe3) which asymmetrically encapsulate a central electrophilic Au(I). |
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