Reversible Oxidative Addition of Zinc Hydride at a Gallium(I)‐Centre: Labile Mono‐ and Bis(hydridogallyl)zinc Complexes

In the presence of TMEDA (N,N,N’,N’‐tetramethylethylenediamine), partially deaggregated zinc dihydride as hydrocarbon suspensions react with the gallium(I) compound [(BDI)Ga] (I, BDI={HC(C(CH(3))N(2,6‐iPr(2)‐C(6)H(3)))(2)}(−)) by formal oxidative addition of a Zn−H bond to the gallium(I) centre. Dissociation of the labile TMEDA ligand in the resulting complex [(BDI)Ga(H)−(H)Zn(tmeda)] (1) facilitates insertion of a second equiv. of I into the remaining Zn−H to form a thermally sensitive trinuclear species [{(BDI)Ga(H)}(2)Zn] (2). Compound 1 exchanges with polymeric zinc dideuteride [ZnD(2)](n) in the presence of TMEDA, and with compounds I and 2 via sequential and reversible ligand dissociation and gallium(I) insertion. Spectroscopic and computational studies demonstrate the reversibility of oxidative addition of each Zn−H bond to the gallium(I) centres.