Oxidative addition or Werner coordination complex? Reactivity of β-diketiminate supported main group and first-row transition metal complexes towards ammonia.

A series of neutral LM (L = [HC{(H 3 C)C(Dipp)N} 2 ], Dipp = 2,6- i Pr 2 C 6 H 3 , M = group 13: B-In, TM: Fe, Co, Ni, Cu) and L'M (L' = [HC{(CCH 2 )(CCH 3 )(DippN) 2 }], M = group 14: C-Pb) compounds including a main group 13/14 and first-row transition metal complexes were studied computationally by density functional theory (DFT). The optimised complexes were assessed in terms of structural parameters and electronic structures to find trends and characteristics that could be used to predict their reactivity towards ammonia. In addition, the differences in oxidative addition and Werner coordination complex formation depending on the identity of the central element were investigated and the Werner complexes were evaluated by QTAIM and EDA-NOCV approaches. The computational results complement the earlier experimental studies and shed light on the feasibility of isolating novel main group Werner complexes or transition metal oxidative addition products.