Abstract
Reactions of [( η 5-R)Rh(CO) 2] (R = cp, ind) with water-soluble phosphines (L = 1,3,5-triaza-7-phosphaadamantane and tris(2-cyanoethyl)phosphine) give the new rhodium(I) complexes of the types [Rh( η 5-cp)(CO)(PTA)] ( 1), [Rh( η 5-cp)(CO)(P(CH 2CH 2CN) 3)] ( 2), [Rh( η 5-ind)(CO)(PTA)] ( 3) and [Rh( η 5-ind)(CO)(P(CH 2CH 2CN) 3)] ( 4) in isolated yields of 52–75%. All these compounds have been fully characterized by IR, 1H, 31P{ 1H} and 13C{ 1H} NMR, FAB-MS spectroscopies and elemental analyses. Reactivity for the substitution of phosphine is greater for [( η 5-ind)Rh(CO)(L)] comparing to [( η 5-cp)Rh(CO)(L)] because of a flexibility of the indenyl ligand to undergo facile η 5– η 3 coordinative isomerizations. The obtained complexes are active catalyst precursors for the dehydrogenation of propan-2-ol, octane and cyclooctane under photoassisted conditions without any organic hydrogen transfer acceptors, giving TOFs of 26–56 using 3 as precatalyst.
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