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Structures and Reactivity Patterns of Group 9 Metallocorroles

Palmer, Joshua H. and Mahammed, Atif and Lancaster, Kyle M. and Gross, Zeev and Gray, Harry B. (2009) Structures and Reactivity Patterns of Group 9 Metallocorroles. Inorganic Chemistry, 48 (19). pp. 9308-9315. ISSN 0020-1669. http://resolver.caltech.edu/CaltechAUTHORS:20091013-093451813

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Abstract

Group 9 metallocorroles 1-M(PPh_3) and 1-M(py)_2 [M = Co(III), Rh(III), Ir(III); 1 denotes the trianion of 5,10,15-tris-pentafluorophenylcorrole] have been fully characterized by structural, spectroscopic, and electrochemical methods. Crystal structure analyses reveal that average metal−N(pyrrole) bond lengths of the bis-pyridine metal(III) complexes increase from Co (1.886 Å) to Rh (1.957 Å)/Ir (1.963 Å); and the average metal−N(pyridine) bond lengths also increase from Co (1.995 Å) to Rh (2.065 Å)/Ir (2.059 Å). Ligand affinities for 1-M(PPh_3) axial coordination sites increase dramatically in the order 1-Co(PPh_3) < 1-Rh(PPh_3) < 1-Ir(PPh_3). There is a surprising invariance in the M(+/0) reduction potentials within the five- and six-coordinate corrole series, and even between them; the average M(+/0) potential of 1-M(PPh_3) is 0.78 V vs Ag/AgCl in CH_2Cl_2 solution, whereas that of 1-M(py)_2 is 0.70 V under the same conditions. Electronic structures of one-electron-oxidized 1-M(py)_2 complexes have been assigned by analysis of electron paramagnetic resonance spectroscopic measurements: oxidation is corrole-centered for 1-Co(py)_2 (g = 2.008) and 1-Rh(py)_2 (g = 2.003), and metal-centered for 1-Ir(tma)_2 (g_(zz) = 2.489, g_(yy) = 2.010, g_(xx) = 1.884, g_(av) = 2.128) and 1-Ir(py)_2 (g_(zz) = 2.401, g_(yy) = 2.000, g_(xx) = 1.937, g_(av) = 2.113).


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http://dx.doi.org/10.1021/ic901164rDOIUNSPECIFIED
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Additional Information:Copyright © 2009 American Chemical Society. Received June 17, 2009. Publication Date (Web): September 8, 2009. This work was supported by the Center for Chemical Innovation Grant NSF CHE-0802907, U.S.−Israel BSF (Z.G. and H.B.G.), BP, CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation. We thank Dr. Angelo Di Bilio for help with measurements of low-temperature EPR spectra; and Drs. Lawrence M. Henling and Michael W. Day for assistance with the acquisition and analysis of crystallographic data. Supporting Information: Additional information as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.
Group:CCI Solar Fuels
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Funding AgencyGrant Number
NSFCHE-0802907
U.S.−Israel Binational Science FoundationUNSPECIFIED
BPUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20091013-093451813
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20091013-093451813
Official Citation:Structures and Reactivity Patterns of Group 9 Metallocorroles Joshua H. Palmer, Atif Mahammed, Kyle M. Lancaster, Zeev Gross, Harry B. Gray Inorganic Chemistry 2009 48 (19), 9308-9315
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16309
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:18 Oct 2009 23:43
Last Modified:03 Apr 2014 22:17

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