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Pentamethylcyclopentadienyl rhodium complexes

Blakemore, James D. and Hernandez, Emilia S. and Sattler, Wesley and Hunter, Bryan M. and Henling, Lawrence M. and Brunschwig, Bruce S. and Gray, Harry B. (2014) Pentamethylcyclopentadienyl rhodium complexes. Polyhedron, 84 . pp. 14-18. ISSN 0277-5387.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle ItemCambridge Structural Database
Blakemore, James D.0000-0003-4172-7460
Sattler, Wesley0000-0001-5316-260X
Hunter, Bryan M.0000-0001-8559-9304
Brunschwig, Bruce S.0000-0002-6135-6727
Gray, Harry B.0000-0002-7937-7876
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).
Group:CCI Solar Fuels
Funding AgencyGrant Number
NSF Postdoctoral FellowshipUNSPECIFIED
Subject Keywords:Vinyl bipyridine; Thallium formate reduction; Crystallographic characterization; Electronic absorption spectra; Metal-to-ligand charge transfer
Record Number:CaltechAUTHORS:20150115-100257213
Persistent URL:
Official Citation:James D. Blakemore, Emilia S. Hernandez, Wesley Sattler, Bryan M. Hunter, Lawrence M. Henling, Bruce S. Brunschwig, Harry B. Gray, Pentamethylcyclopentadienyl rhodium complexes, Polyhedron, Volume 84, 14 December 2014, Pages 14-18, ISSN 0277-5387, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53768
Deposited By: Tony Diaz
Deposited On:15 Jan 2015 23:36
Last Modified:09 Mar 2020 13:18

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