Metal-induced BH activation. Addition of phenylacetylene to Cp*Rh-, Cp*Ir-, ( p -cymene)Ru- and ( p -cymene)Os halfsandwich complexes containing a chelating 1,2-dicarba- closo -dodecaborane-1,2-dichalcogenolate ligand

摘要: Abstract The addition reactions of the 16e halfsandwich complexes Cp*M[S 2 C (B 10 H )] ( 1S M=Rh, 2S M=Ir) and η 6 -(4-isopropyltoluene)M[S 3S M=Ru 4S M=Os) with phenylacetylene lead selectively to 18e 5S – 8S , in which a metalboron bond is present regio- stereoselectively inserted into one MS bonds, hydrogen atom transferred from carborane cage terminal carbon alkyne, corresponding ortho -metalation cage. In all cases, S-η -(Ph)CC C(1)B units are linked metal cisoid positions. analogous reaction Cp*Ir[Se 2Se gives 6Se . Complex undergoes an intramolecular rearrangement solution isomer 9S where RhB cleaved, B-atom now bearing organic substituent, metalcarbon σ being formed together coordinative S→Rh bond. contrast, p -cymene 7S rearrange isomers 10S 11S -(Ph)CC C(1)B(M) moieties occupy transoid positions, preventing further rearrangements. proposed structures were deduced NMR data 1 H-, 11 B-, 13 C-, 77 Se-, 103 Rh-NMR) X-ray structural analyses carried out for