Lability of Ta-NHC adducts as a synthetic route towards heterobimetallic Ta/Rh complexes

We report the synthesis and characterization of a series of original tantalum/rhodium heterobimetallic species assembled by a bifunctional alkoxy-N-heterocyclic carbene (NHC) ligand platform (noted L). The heterotrimetallic [Ta(CH2tBu)(CHtBu)(μ-L)Rh2(COD)2Cl2]n, 2, and heterobimetallic [Ta(μ-L)(CHtBu)(CH2tBu)2Rh(COD)Cl], 4, complexes are obtained upon treatment of [Ta(L)(CHtBu)(CH2tBu)2], 1, with [Rh(COD)Cl]2. To avoid parasistic reactivity arising from the neopentylidene fragment in 1, the peralkyl compound {Ta(L)[OSi(OtBu)3](CH2tBu)3}, 5, resulting from the 1,2-addition of tris(tertbutoxysilanol) across the Ta[double bond, length as m-dash]C alkylidene motif, is prepared. An unanticipated silanol-NHC adduct, {HOSiOtBu3}{Ta(L)[OSi(OtBu)3](CH2tBu)3}, 6, is formed when 1 is treated with two equivalents of HOSi(OtBu)3. Finally, treatment of 5 with [Rh(COD)Cl]2 provides the heterobimetallic complex {Ta(μ-L)[OSi(OtBu)3](CH2tBu)3Rh(COD)(Cl)}, 7, in high yield. This work highlights the reactivity of Ta-NHC adducts and the aptitude of the NHC motif to transfer from Ta to Rh which is used with profit as an efficient synthetic route to access early/late heterobimetallic complexes.