Synthesis and reactivity of the novel hydride derivative RhHCl(TIMP3) (HTIMP3 = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane)
The reaction of HTIMP(3) (HTIMP(3) = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane) with [RhCl(COD)](2) and Rh(acac)(CO)(2) produces RhHCl(TIMP(3)) (1H) and Rh(TIMP(3))(CO) (2), respectively, both exhibiting tetradentate kappaC,kappa(3)P-coordination of the TIMP(3) moiety. The reaction of RhHCl(TIMP(3)) with nucleophiles (L) in the presence of AgBF(4) or AgPF(6) produces different compounds depending on the nature of L. Indeed, cationic Lewis adducts of formula [RhH(L)(TIMP(3))](+) ((2H+)-(5H+)) are obtained when L is CO, CNCH(2)Ph, pyridine or CH(2)CHCN. On the other hand, when the incoming nucleophile is CH(3)COOH the hydride-free complex [Rh(CH(3)COO)(TIMP(3))](+) ((6+)) is o…
An Unprecedented Iridium(III) Catalyst for Stereoselective Dimerisation of Terminal Alkynes
A novel iridium(III) hydride complex, IrHCl(TIMP 3 ) {HTIMP 3 = tris[1-(diphenylphosphino)-3-methyl-lH-indol-2-yl]methane) was prepared and fully characterized in both the solid state and in solution. Chloride abstraction by silver cations provides a more reactive compound, [IrH-(TIMP 3 )][BF 4 ], which can react with pyridine (py) and phenylacetylene to yield the complexes [IrH-(TIMP 3 )(py)][BF 4 ] and [Ir(PhCH=C-CH=CHPh)-(TIMP 3 )][BF 4 ], respectively. Interestingly, IrH-(TIMP 3 )(py)][BF 4 ] efficiently catalyses the stereoselective dimerisation of model terminal alkynes to the 1,4-disubstituted (E)-but-1-en-3-yne only.