Organorhodium chemistry

[2] Rhodium(0) complexes are binary carbonyls, the principal examples being tetrarhodium dodecacarbonyl, Rh4(CO)12, and hexadecacarbonylhexarhodium, Rh6(CO)16.

The sandwich compound rhodocene is one example, even it exists in equilibrium with a dimeric Rh(I) derivative.

Strong donor ligands - hydride, silyl, boryl - are required to stabilize Rh(V).

Although such compounds are well documented in the literature rhodium(III) cyclometalates with azo function are spare.

novel hexacoordinated orthometalated rhodium(III) thiolato complex trans-[Rh(C∧N∧S)Cl(PPh3)2] was synthesized from benzyl 2-(phenylazo)phenyl thioether and RhCl3·3H2O in the presence of excess PPh3 via in situ C(sp2)−H and C(sp3)−S bond scissions.

The mechanism of formation of orthometalated azobenzene derivative was described to proceed via initial coordination of azo-nitrogen followed by electrophilic substitution at the pendant phenyl ring.

Unlike analogous (phenylazo)phenolato compound the orthometalated thiolato complex exhibits a fully reversible oxidative wave at 0.82 V vs Ag/AgCl and this response is supposed to be primarily centered on the thiolato sulfur atom.

Cationic organorhodium(I) catalysts are useful for asymmetric hydrogenations, which are applied to bioactive products such as pharmaceutical agents and agrochemicals.

Cyclooctadiene rhodium chloride dimer
Rh-catalyzed borylation reactions involve Rh(V) intermediates.
The catalytic cycle of the Monsanto process for production of acetic acid.
A rhodium-based hydroformylation catalyst, where PAr 3 = triphenylphosphine or its sulfonated analogue Tppts .
Structure of [Rh( DIPAMP )( cod )] + , a precatalyst for asymmetric hydrogenation. [ 11 ]