| Abstrakt: |
The thorium bipyridyl metallocene (Cp3tBu)2Th(bipy) (1; Cp3tBu= η5-1,2,4-(Me3C)3C5H2) shows a rich reactivity toward a series of small molecules. For example, complex 1may act as a synthon for the (Cp3tBu)2Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH)2, Ph2E2(E= S, Se), elemental sulfur (S8) and selenium (Se), organic azides, CS2, and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones Ph2CO and (CH2)5CO, aldehydes p-MePhCHO and p-ClPhCHO, seleno-ketone (p-MeOPh)2CSe, nitriles PhCN, Ph2CHCN, C6H11CN, and p-(NC)2Ph, and benzoyl cyanide PhCOCN, C–C coupling occurs to furnish (Cp3tBu)2Th[(bipy)(Ph2CO)] (10), (Cp3tBu)2Th[(bipy)((CH2)5CO)] (11), (Cp3tBu)2Th[(bipy)(p-MePhCHO)] (12), (Cp3tBu)2Th[(bipy)(p-ClPhCHO)] (13), (Cp3tBu)2Th[(bipy){(p-MeOPh)2CSe}] (14), (Cp3tBu)2Th[(bipy)(PhCN)] (16), (Cp3tBu)2Th[(bipy)(Ph2CHCN)] (17), (Cp3tBu)2Th[(bipy)(C6H11CN)] (18), [(Cp3tBu)2Th]2{μ-(bipy)[p-Ph(CN)2](bipy)} (20), and (Cp3tBu)2Th{(bipy)[PhC(CN)O]} (21), respectively. Nevertheless, ketazine (PhCH═N)2or benzyl nitrile PhCH2CN forms the dimeric complexes [(Cp3tBu)Th]2[μ-NC(Ph)(bipy)]2(15) and (Cp3tBu)2Th[(bipy){C(═CHPh)NH}] (19), respectively. In contrast, C–N bond cleavage and C–C coupling processes occur upon addition of isonitriles Me3CNC and C6H11NC to 1to yield the thorium isocyanido amido complexes (Cp3tBu)2Th[4-(Me3C)bipy](NC) (22) and (Cp3tBu)2Th[4-(C6H11)bipy](NC) (23), respectively. Furthermore, a single-electron transfer (SET) process ensues when 1 equiv of CuI is added to 1to yield the Th(VI) bipyridyl iodide complex (Cp3tBu)2Th(I)(bipy) (3). |
