Crystal structures of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) monohydrate and fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs.

Joseph S Merola,Marion A Franks

doi:10.1107/s2056989015001516

Abstract

The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

Highlights

The crystal structures of two solvates of fac-trichloridotris(trimethylphosphaneP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac[RhCl3(Me3P)3]H2O, and one with methanol in the crystal lattice, fac[RhCl3(Me3P)3]0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al (2013)
Chlorido compounds of rhodium and iridium with phosphane ligands provide important starting materials for other metal complexes of that family through replacement of the chlorine
This paper adds to the body of knowledge of rhodium complexes that complement the already published structures of the analogous iridium compounds

Summary

Chemical context

Phosphane complexes of noble metals, especially those of rhodium and iridium, have proven to be important in catalysis as well as in studying fundamental reactions at metal surfaces. We have shown that (Me3P)3IrCl3 can be converted into (Me3P)3IrMe3 through reaction with methylmagnesiumchloride. This trimethyliridium compound can, in turn, be used to study organometallic reactions at the iridium(III) atom (Merola et al, 2013). This paper adds to the body of knowledge of rhodium complexes that complement the already published structures of the analogous iridium compounds. It contributes to the information on crystal structures of L3MCl3 compounds, comparing the rhodium structures to the iridium structures as well as confirming the nature of solvate formation in both the iridium and rhodium structures. Displacement ellipsoid (50% probability level) rendering of the fac-trichloridotris(trimethylphosphane)rhodium–water compound, RhP3Cl3water

Structural commentary

Database survey

Supramolecular features

Findings

Synthesis and crystallization