Nickelapnicogencubane

Nickelapnicogencubanes The thermolysis of [C*pNi(CO))] 2 ( 1 ) (C*p=η 5 ‐C 5 Me 5 ) and [Cp′Ni(CO)] 2 ( 6 ) (Cp′ = η 5 ‐C 5 H 4 Me) with the pnicogens E 4 (E = P, As) affords the distorted cubanes [(C*pNi) 3 (μ 3 ‐E)(E 4 )] ( 2a : E = P; 2b : E = As), the sandwich complex [C*pNi(η 3 ‐P 3 )] ( 3 ), as well as the cubanes [Cp′Ni(μ 3 ‐E)] 4 ( 7a,b ) and the trinuclear cluster [(Cp′Ni) 3 (μ 3 ‐CO) 2 ] ( 8 ). With [M(CO) 5 (thf)], 2a and 3 give the multinuclear clusters [(C*pNi) 3 (μ 3 ‐P)(P 4 )M(CO) 5 ] ( 4a : M = CR; 4b : M = Mo; 4c : M = W) as well as [C*pNi(P 3 )‐{Cr(CO) 5 } 3 ] ( 5 ). In addition to the NMR studies, 2a,b and 3 have been characterized by X‐ray structure analyses.