1. The bicluster oxidative addition as a route to bicapped hexaplatinum clusters
- Author
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Richard J. Puddephatt, Leijun Hao, Greg J. Spivak, Ljubica Manojlović-Muir, Jagadese J. Vittal, Kenneth W. Muir, and Dmitrii S. Yufit
- Subjects
Inorganic Chemistry ,Crystallography ,Trigonal prism ,Chemistry ,Materials Chemistry ,Cluster (physics) ,Crystal structure ,Physical and Theoretical Chemistry ,Trigonal prismatic molecular geometry ,Oxidative addition ,Monoclinic crystal system - Abstract
The reaction of either the 84-electron cluster [Pt 6 (μ-CO) 6 (μ-dppm) 3 ] ( 1 ) or the 82-electron cluster [Pt 6 (CO) 6 (μ-dppm) 3 ] 2+ ( 2 ), dppm = Ph 2 PCH 2 PPh 2 , with SnX 3 − or Hg 2 X 2 gave the corresponding bicapped trigonal prismatic 86-electron clusters [Pt 6 ( μ 3 -SnX 3 ) 2 ( μ -CO) 6 ( μ -dppm) 3 ] ( 3 : X = F( 3a , Cl( 3b ), Br( 3e ) or [ Pt 6 (μ 3 - HgX ) 2 (μ- CO ) 6 (μ- dppm ) 3 ] 4 : X = Cl ( 4a ) , Br ( 4b ), l ( 4c ), respectively. The new clusters 3 and 4 have been characterized spectroscopically and 4c has also been characterized by X-ray diffraction. Crystals of 4c·CH 2 Cl 2 ·2Et 2 O are monoclinic, space group P 2 1 c , a=20.092(9), b=18.718(7), c=26.258(7) A , β=108.09(3)° V=9387(6) A 3 , Z =4. The molecular core in 4c is a Pt 6 trigonal prism with each triangular Pt 3 face capped by an Hgl fragment. The intertriangle PtPt bond distances (2.910(1)–2.948(1) A) are longer than the intratriangle PtPt distances (2.634(1)–2.687(1) A) and this is consistent with EHMO calculations. The reaction of 1 with Hg 2 X 2 to give 4 is termed a bicluster oxidative addition; according to predictions from EHMO calculations it should lead to stronger intertriangle PtPt bonding in 3 and 4 than in the precursor cluster 1 , but this is not suppored by structural data observed in 3c and 4c .
- Published
- 1997