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Synthesis and structural analysis of the first nanosized platinum-gold carbonyl/phosphine cluster, Pt13[Au2(PPh3)2]2(CO)10(PPh3)4, containing a Pt-centered [Ph3PAu-AuPPh3]-capped icosahedral Pt12 cage
被引:39
作者:
de Silva, N
[1
]
Dahl, LF
[1
]
机构:
[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词:
D O I:
10.1021/ic050990v
中图分类号:
O61 [无机化学];
学科分类号:
070301 ;
081704 ;
摘要:
The preparation and molecular structure of the initial nanosized platinum-gold carbonyl cluster, Pt-13[Au-2(PPh3)(2)](2)(CO)(10)(PPh3)(4) (1), are described. A comparative analysis reveals its pseudo-D-2h geometry, consisting of a centered Pt-13 icosahedron encapsulated by two centrosymmetrically related bidentate [Ph3PAu-AuPPh3]-capped ligands along with 4 PR3 and 10 CO ligands, to be remarkably similar to that of the previously reported Pt-17(mu(2)-CO)(4)-(CO)(8)(PEt3)(8) (2). Reformulation of 2 as Pt-13[(PtPEt3)(2)(mu(2)-CO)](2)-(CO)(10)(PEt3)(4) emphasizes the steric/electronic resemblance of the bulky-sized bidentate [Ph3PAu-AuPPh3] and [(PtPEt3)(2)(mu(2)-CO)] capping ligands in 1 and 2, respectively, as well as their identical electron counts of 162 cluster valence electrons for a centered Pt-13 icosahedron. We hypothesize that analogous steric effects of their ligand polyhedra in 1 and 2 play a crucial role along with electronic effects in the formation and stabilization of these two nanosized clusters that contain an otherwise unknown centered icosahedron of platinum atoms.
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页码:9604 / 9606
页数:3
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