Protonolysis of [ZnH 2 ] n with the conjugated Brønsted acid of the bidentate diamine TMEDA(N,N,N',N'tetramethylethane-1,2-diamine) and TEEDA(N,N,N',N'-tetraethylethane-1,2-diamine) gave the zinc hydride cation [(L 2)ZnH] + ,i solable either as the mononuclear THF adduct [(L 2)ZnH(thf)] + [BAr F 4 ] À (L 2 = TMEDA; BAr F 4 À = [B-(3,5-(CF 3) 2-C 6 H 3) 4 ] À)o ra st he dimer [{(L 2)Zn)} 2 (m-H) 2 ] 2+-[BAr F 4 ] À 2 (L 2 = TEEDA). In contrast to [ZnH 2 ] n ,the cationic zinc hydrides are thermally stable and soluble in THF. [(L 2)ZnH] + was also shown to form di-and trinuclear adducts of the elusive neutral [(L 2)ZnH 2 ]. All hydride-containing cations readily inserted CO 2 to give the corresponding formate complexes.[ (TMEDA)ZnH] + [BAr F 4 ] À catalyzedt he hydrosilylation of CO 2 with tertiary hydrosilanes to give stepwise formoxys ilane,m ethyl formate,a nd methoxy silane.T he unexpected formation of methyl formate was shown to result from the zinc-catalyzed transesterification of methoxy silane with formoxys ilane,w hichw as eventually converted into methoxy silane as well.
The palladium diphosphinoboryl pincer [{(o-PPhCH)B}PdI] 8 was prepared from the diphosphinoborane complex 6a. The boryl functionality of the pincer displayed ambiphilic properties allowing: (1) coordination of Lewis basic pyridines to the boryl site and (2) access to palladium diphosphinoborane complex derivatives.
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