The use of CoCl2(amidine)2 compounds in the synthesis of tetragonal lantern dicobalt compounds: synthesis, structures and theoretical studies of Co2(DPhF)4 and the oxidized species [Co2(DPhBz)4
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- 作者：Cotton ; F. Albert ; Daniels ; Lee M. ; Xuejun ; Feng ; Maloney ; David J. ; Matonic ; John H. ; Murillo ; Carlos A.
- 关键词：Crystal structures ; Cobalt complexes ; Amidinate complexes ; Tetragonal 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：291-301
- 全文大小：1001 K
文摘
CoCl2(PhNC(R)N(H)Ph)2 complexes (R = H and Ph) have been reacted with methyllithium to produce the corresponding lantern-type Co2(amidinato)4 compounds containing cobalt-cobalt bonds of order one. One of them, Co2(DPhBz)4 (DPhBz = diphenylbenzamidinato), was oxidized by AgPF6 to yield [Co2(DPhBz)4](PF6) · 2.4CH2Cl2. Crystal data for Co2(DPhF)4 (I) (DPhF = diphenylformamidinato) at 0°C are: monoclinic, space group C2/c, a = 13.927(3), b = 13.678(3), c = 22.855(5) Å, β = 91.37(2)°, Z = 4. For [Co2(DPhBz)4]-(PF6) · 2.4CH2Cl2 (II) at −60°C: triclinic, space group P1, a = 13.838(4), b = 13.881(4), c = 19.62(1) Å, α = 89.7(1), β = 99.76(4), γ = 91.04(4)°, Z = 2. The metal-to-metal distances are 2.3735(9) Å for complex I and 2.322(2) and 2.332(2) Å for two crystallographically independent molecules found in complex II. The latter are slightly longer than those found in the parent neutral molecule. The experimental cobalt-to-cobalt separations are in good agreement with those obtained from ab initio quantum chemical calculations.