A series of triflylamide-tethered Cp 0 Rh and Cp 0 Ir complexes, [η 5 :η 1 -(CH 3 ) 4 C 5 (CH 2 ) n NTf]M (M = Rh, Ir, n = 2-4), have been newly prepared and their three-legged pianostool structure has been characterized. The tethered complexes having the (R,R)-MsDPEN ligand have been found to promote asymmetric hydrogenation of acetophenone, which indicates that the introduction of a suitable triflylamide tether unit changes their catalytic function from transfer hydrogenation to hydrogenation.
A series of mononuclear tethered complexes, RhIII(η5:η1-Cp′-NHR), in which the η5-peralkylcyclopentadienyl group and the ligated protic amine group are connected by suitable carbon chains, were newly prepared and structurally characterized. Their catalytic performance in the reductive amination of carbonyl compounds was significantly influenced by the chain length of the tether, which possibly plays a key role in determining the reaction course.
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