Synthesis and Structure of [η-1,2,4-(MeSi)CH]Th(bipy) and Its Reactivity toward Small Molecules.

Halide exchange of (Cp)ThCl (; Cp = η-1,2,4-(MeSi)CH) with MeSiI furnishes (Cp)ThI (), which is then reduced with potassium graphite (KC) in the presence of 2,2'-bipyridine to give the thorium bipyridyl metallocene (Cp)Th(bipy) () in good yield. Complex was fully characterized and readily reacted with various small molecules. For example, may serve as a synthetic equivalent for the (Cp)Th(II) fragment when exposed to CuI, PhS, organic azides, and CS. Moreover, upon the addition of thiobenzophenone PhCS, -methylbenzaldehyde (-MeCH)CHO, benzophenone PhCO, amidate PhCONH(-tolyl), seleno-ketone (,'-dimethoxy), selenobenzophenone (-MeOPh)CSe, di(-tolyl)methanimine (-tolyl)C═NH, 1,2-di(benzylidene)hydrazine (PhCH═N), and nitriles PhCN, PhCHCN, and PhCHCN C-C coupling results to give (Cp)Th[(bipy)(PhCS)] (), (Cp)Th[(bipy)(-MePhCHO)] (), (Cp)Th[(bipy)(PhCO)] (), (Cp)Th[(bipy){(-tolylNH)(Ph)CO}] (), (Cp)Th[(bipy){(-MeOPh)CSe}] (), (Cp)Th[(bipy){(-tolyl)CNH}] (), (Cp)Th[(bipy)(PhCHNN═CHPh)] (), (Cp)Th[(bipy)(PhCN)] (), (Cp)Th[(bipy)(PhCHCN)] (), and (Cp)Th[(bipy)(PhCHCN)] (), respectively. However, when thiazole is added to , the dimeric sulfido complex [(Cp)Th][μ-(bipy)CHNCHCHS] () can be isolated. Moreover, the addition of isonitriles such as MeCNC and PhCHNC to results in C-N bond cleavage and C-C coupling processes to form the thorium isocyanido amido complexes (Cp)Th4-(MeC)bipy () and (Cp)Th4-(PhCH)bipy (), respectively. Nevertheless, upon exposure of to (trimethylsilyl)diazomethane MeSiCHN, the bis-amido complex (Cp)Th[5,6-(MeSiCH)bipy] (), concomitant with N release, is isolated.