Synthese,Strukturuntersuchung und Koordinationschemie von Isocyanacetonitril

Synthesis, Structure, and Coordination Chemistry of Isocyanoacetonitrile Isocyanoacetonitrile 1 was synthesized starting from aminoacetonitrile by the Ugi method. The structure and relative energies of 1 were calculated by ab initio methods (MP2/6‐31G**) in comparison with malonodinitrile and diisocyanomethane. 1 crystallizes on cooling below –14 °C forming a colourless solid, monoclinic, Pn, a = 614.9(2), b = 756.3(1), c = 786.4(3) pm, β = 98.99(4)°, Z = 4, R = 0.054, wR₂ = 0.132, with two molecules representing the asymmetric unit. 1 polymerizes readily at ambient temperature forming a dark‐brown almost insoluble solid 2 . 1 can be stabilized by coordination to metal fragments. The metal complexes (CO)₅M(CNCH₂CN) ( 3 ) ( a , M = Cr; b , M = W), CpMn(CO)₂(CNCH₂CN) ( 4 ) and fac‐(CO)₃W(CNCH₂CN)₃ ( 5 ) were synthesized and characterized by spectroscopic methods. The structures of 3 a , monoclinic, C2/c, a = 2481.4(7), b = 582.2(2), c = 2053.3(6) pm, β = 134.57(2)°, R₁ = 0.0368, wR₂ = 0.1001, and 4 , monoclinic, P2₁/a, a = 1223.7(2), b = 586.0(1), c = 1446.3(3) pm, β = 97.81(2)°, R₁ = 0.0459, wR₂ = 0.1190, were determined by single crystal X‐ray diffraction.