Homoleptic Hexa and Penta Gallylene Coordinated Complexes of Molybdenum and Rhodium
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- 作者：Timo Bollermann ; Thomas Cadenbach ; Christian Gemel ; Kerstin Freitag ; Mariusz Molon ; Vanessa Gwildies ; Roland A. Fischer
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：June 20, 2011
- 年：2011
- 卷：50
- 期：12
- 页码：5808-5814
- 全文大小：866K
- 年卷期：v.50,no.12(June 20, 2011)
- ISSN：1520-510X
文摘
The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC6H3-2,6-iPr2)2) were investigated and compared. Treatment of [Mo(畏4-butadiene)3] with GaCp* under hydrogen atmosphere at 100 掳C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)6] (1) in good yields 鈮?0%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa6] core. Similarly, [Rh(GaCp*)5][CF3SO3] (2) and [Rh(GaCp*)5][BArF] (3) (BArF = B{C6H3(CF3)2}4) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe)2(CF3SO3)]2 (coe = cyclooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa5] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)2(CF3SO3)]2 does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF3SO3)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF3SO2O路路路Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature 1H and 13C NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.