The 2-coordinate d9 and d10 bis(trimethylsilyl) amides and (IPr)M-N(SiMe3)2 (M=Ni, Cu) have been prepared and feature planar amide structures with an extremely nucleophilic N-lone-pair. As a consequence, they undergo nucleophilic addition at the acidic carbon in the heterocumulenes CO2 and RN=C=O with elimination of O(SiMe3)2 and addition of the ��(IPr)M-N2�� fragment to carbon. The reactions with CO2 give {(IPr)Ni(�-NCO)}2 and (IPr)Cu-NCO, with the d9 Ni derivative dimerizing. The mixed t-Bu/SiMe3 amide complex (IPr)Ni-N(SiMe3)tBu, having only one migrating silyl substituent, gives (IPr)Ni-N(tBu)C(O)OSiMe3 in its reaction with CO2 supporting direct nucleophilic attack of N at C. Benzylisocyanate reacts similarly to form metallacarbodiimides {(IPr)Ni-N=C=NCH2Ph}2 and (IPr)Cu-N=C=NCH2Ph (bridging for d9 Ni, terminal for d10 Cu) and O(SiMe3)2. The reactivity of the Cu amide will be compared with that of the phosphide analogue (IPr)Cu-P(SiMe3)2.

Reactions of two-coordinate amido complexes of Ni and Cu with CO<sub>2</sub> and RNCO

245th National Meeting (2013)

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Reactions of two-coordinate amido complexes of Ni and Cu with CO2 and RNCO

Reactions of two-coordinate amido complexes of Ni and Cu with CO₂ and RNCO