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Rhodium and Iridium Complexes Bearing "Capping Arene" Ligands: Synthesis and Characterization

Gu, Shunyan and Musgrave, Charles B., III and Gehman, Zoë M. and Zhang, Ke and Dickie, Diane A. and Goddard, William A., III and Gunnoe, T. Brent (2021) Rhodium and Iridium Complexes Bearing "Capping Arene" Ligands: Synthesis and Characterization. Organometallics, 40 (16). pp. 2808-2825. ISSN 0276-7333. doi:10.1021/acs.organomet.1c00250.

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A series of olefin-coordinated RhI and IrI complexes bearing “capping arene” ligands (5-^XFP and 6-^XFP, see below) of the general formulas (FP)M(olefin)X, [(FP)M(olefin)₂][M(olefin)₂X₂], and [(FP)M(olefin)₂]BF₄ (FP = “capping arene” ligands, X = halide or pseudohalide, olefin = ethylene, cyclooctene, (olefin)₂ = (C₂H₄)₂ or cyclooctadiene) were synthesized and characterized. Single-crystal X-ray diffraction studies revealed structural differences that are a function of the identity of the capping arene ligand and the metal. For 5-^XFP ligands (5-^XFP = 1,2-bis(N-7-azaindolyl)-benzene and derivatives with substituents on the arene moiety), the coordination to both Rh and Ir gives rise to complexes that are best described as 16-electron and square planar. For 6-^XFP ligands (6-^XFP = 8,8′-(1,2-phenylene)diquinoline and derivatives with substituents on the arene moiety), the structures of Rh and Ir complexes are better considered as 18-electron and trigonal bipyramidal due to an η²-C,C interaction between the metal center and the arene group of the capping arene ligand. Variable-temperature ¹H NMR spectroscopy studies of ethylene rotation demonstrated that the Ir complexes possess higher activation barriers to rotation in comparison to Rh complexes and the 6-^XFP complexes tend to give ethylene higher rotational barriers in comparison to 5-^XFP complexes for complexes of the type (FP)Rh(η²-C₂H₄)Cl. DFT calculations are consistent with enhanced Rh to ethylene π-back-donation for Rh complexes ligated by the 6-^XFP ligands in comparison to the 5-^XFP ligands.

Item Type:Article
Related URLs:
URLURL TypeDescription
Gu, Shunyan0000-0002-3625-1042
Musgrave, Charles B., III0000-0002-3432-0817
Gehman, Zoë M.0000-0002-2181-6055
Zhang, Ke0000-0001-8090-7179
Dickie, Diane A.0000-0003-0939-3309
Goddard, William A., III0000-0003-0097-5716
Gunnoe, T. Brent0000-0001-5714-3887
Additional Information:© 2021 American Chemical Society. Received: April 23, 2021; Published: August 3, 2021. The Gunnoe group acknowledges support from the U.S. National Science Foundation (CHE-1800173). C.B.M. and W.A.G. received support from ONR (N00014-19-1-2081). The authors declare no competing financial interest.
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-19-1-2081
Subject Keywords:Chemical structure, Hydrocarbons, Transition metals, Metals, Ligands
Issue or Number:16
Record Number:CaltechAUTHORS:20210823-222134173
Persistent URL:
Official Citation:Rhodium and Iridium Complexes Bearing “Capping Arene” Ligands: Synthesis and Characterization. Shunyan Gu, Charles B. Musgrave, Zoë M. Gehman, Ke Zhang, Diane A. Dickie, William A. Goddard, and T. Brent Gunnoe. Organometallics 2021 40 (16), 2808-2825; DOI: 10.1021/acs.organomet.1c00250
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110394
Deposited By: Tony Diaz
Deposited On:24 Aug 2021 17:46
Last Modified:24 Aug 2021 17:46

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