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Published December 14, 2014 | Supplemental Material
Journal Article Open

Pentamethylcyclopentadienyl rhodium complexes

Abstract

We report syntheses and structures of pentamethylcyclopentadienyl (Cp∗) rhodium(III) and rhodium(I) complexes. Dicationic rhodium(III) complexes, [Cp∗Rh(bpy)(MeCN)](PF_6)_2 and [Cp∗Rh(vbpy)(MeCN)](PF_6)_2 (bpy = 2,2′-bipyridyl and vbpy = 4-vinyl-2,2′-bipyridyl), were prepared by treatment of [Cp∗Rh(MeCN)_3](PF_6)_2 with bpy and vbpy, respectively. The monocationic rhodium(III) complex, [Cp∗Rh(Me_4phen)Cl]Cl (Me_4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline), was prepared by treatment of the chloride-bridged rhodium dimer, [Cp∗RhCl_2]_2, with Me_4phen. Two rhodium(I) complexes were synthesized via reduction of their rhodium(III) counterparts using two different methods: Cp∗Rh(bpy) was produced via a new route involving treatment of [Cp∗Rh(bpy)Cl]Cl with thallium formate in dry acetonitrile, whereas [Cp∗Rh(Me_4phen)Cl]Cl was reduced with Na(Hg) to give Cp∗Rh(Me_4phen). The colors of the Rh(I) complexes are attributable to relatively intense visible-region MLCT absorptions.

Additional Information

© 2014 Elsevier Ltd. Received 3 April 2014; Accepted 8 May 2014; Available online 20 May 2014. The authors thank Aaron Sattler and Nathan Schley for helpful discussions. This research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and CCI Postdoctoral Fellowships to JDB and WS. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094).

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