The titanium salycilate complex [Cp*Ti(sal)(salH)] 1 (salH(2), = salycilic acid) was synthesised by reacting Cp*TiMe3 and salycilic acid. The molecular structure of 1 studied by X-ray shows it to be dinuclear with a carboxylate group acting as a bridge ligand. [Rh(mu-OH)COD](2) reacts with 1 to yield the bimetallic complex 2, or with the siloxanodiol (HOSiPh)(2)O to yield the bimetalic bis-siloxide Rh complex 3. Carbon monoxide displaces COD in 2 and 3 to give the carbonylic complexes 4 and 5 respectively. Complex 4 can also be prepared from 2 and [Rh(acac)(CO)(2)]. Compounds 2, 3, 4 and 5 can be envisaged as models of Rh complexes anchored on titania or silica. The catalytic performance of heterometallic complexes is studied in the CO hydrogenation reaction and compared to rhodium-based (Rh-based) catalysts prepared by impregnation from Rh(NO3)(3) or [Rh(acac)(CO)2] showing higher yields to oxygenated products. (c) 2005 Elsevier B.V. All rights reserved.