| Institution: | 1. Institute for Inorganic Chemistry, RWTH Aachen University, 52062 Aachen, Germany
Chemistry Research Laboratory, University of Oxford, Oxford, OX1 3TA United Kingdom;2. CNRS, INSA, UPS, UMR 5215, LPCNO, Université de Toulouse, 31077 Toulouse, France;3. Institute for Inorganic Chemistry, RWTH Aachen University, 52062 Aachen, Germany |
| Abstract: | 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(CH3)N(2,6-iPr2-C6H3))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)}2Zn] ( 2 ). Compound 1 exchanges with polymeric zinc dideuteride ZnD2]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. |
