Sterische Stabilisierung von 20-Eletronen-Halbsandwichkomplexen. Die kristallstruktur von [(C5H5)Co{P(OMe)2O}3Ni(C5Ph5]
作者： Wolfgang Kläui , Michael Huhn , Regine Herbst-Irmer
DOI: 10.1016/0022-328X(91)83289-G
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摘要: Abstract The nickel complexes [(C 5 Ph )Ni(CO)Br] and )Ni(CO)(CIO 4 )] react with the sodium salts Na[C H )Co{P(R) 2 O} 3 ] in dichloromethane to yield compounds Ni(C (R = OMe ( 2a ), OEt 2b O i Pr 2c )). crystals of are triclinic, space group Povbar|1 wit a 1226.4(2), b 2014.7(4), c 2047.3(4) pm, α 61.09(3), β 81.33(3), γ 89.56(3)°, Z 4, R 0.042 for 9353 observed reflections. Apart from cyclopentadienyl ring molecules approximateto three-fold symmetry. Three OP(OMe) -units bridge two metal all three phosphoryl oxygen atom-nickel distances being equal. 20-electron compoundsd 2a-c stable at room temperature paramagnetic solution ad solid state. magnetic moment state has been determined, it correponds unpaired electrons. cyclovoltammograms demonstrate that they can be oxidised quasi-reversibly + 0.26 V (vs SCE). cations formed coud not isolated; decompse elimination pentaphenylcyclopentadienyl radical formation (II) complex [{(C )Co[P(R) }Ni]. cyclic voltammogram )Co[P(OEt) O] } Ni] shows reversible (II/III) wave 1.2
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