Dicobalt trigonal lanterns: compounds containing the Co23+ core Co2[RC(NPh)2]3 (R = H, C6H5) and an oxidized compound {Co
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- 作者：Cotton ; F. Albert ; Daniels ; Lee M. ; Maloney ; David J. ; Matonic ; John H. ; Murillo ; Carlos A.
- 关键词：Crystal structures ; Cobalt complexes ; Amidinate complexes ; Trigonal lantern complexes ; Dinuclear complexes
- 刊名：Inorganica Chimica Acta
- 出版年：1997
- 出版时间：March 31, 1997
- 年：1997
- 卷：256
- 期：2
- 页码：283-289
- 全文大小：648 K
文摘
The preparation of two compounds in which a Co23+ core is supported by three bridging amidinato anions is reported. These compounds are: Co2(DPhF)3·0.5toluene (I) and Co2(DPhBz)3 · 0.5toluene (II), where DPhF and DPhBz represent [HC(NPh)2]− and [PhC(NPh)2]−. These dinuclear species are made from CoCl2(HDPhF)2 and CoCl2(HDPhBz)2 by first reducing them with 0.5 equiv. of NaEt3BH and then deprotonating with C4H9Li. A corresponding oxidized form of I, namely [Co2(μ-DPhF)3(MeCN)2]PF6 (III) does not possess a metal-metal bond but contains two distorted tetrahedrally-coordinated Co2+ ions bridged by three amidinate groups. The fourth coordination site of each cobalt ion is occupied by an acetonitrile molecule. Crystallographic data for I are as follows: space group P,a = 11.312(2),b = 12.216(1), c = 14.1680(9) Å, α = 110.700(9), β = 91.860(9), γ = 95.770(9)°, V = 1817.3(4)Å3 and Z = 2. For II: space group P,a = 13.290(3), b = 13.382(3), c = 16.558(3) Å, α = 108.21(3), β = 97.57(3), γ = 116.08(3)°,V = 2384.3(8) Å3 and Z = 2. For III: space group P21/n, a = 14.727(3), b = 16.582(3), c = 18.853(4) Å, β = 105.00(3)°, V = 4447(2) Å3 and Z = 4. A metal-metal bond order of one-half is assigned to I and II for which Co-Co distances are 2.385(1) and 2.3201(9) Å, respectively.