Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published October 5, 2009 | Supplemental Material
Journal Article Open

Structures and Reactivity Patterns of Group 9 Metallocorroles

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).

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.

Attached Files

Supplemental Material - ic901164r_si_001.pdf

Supplemental Material - ic901164r_si_002.pdf

Files

ic901164r_si_002.pdf
Files (1.1 MB)
Name Size Download all
md5:8049af5cf3c1eeebbe65aaa671be5d50
238.6 kB Preview Download
md5:68cbe4cd1c03c48a9d6019e466cc98a6
858.9 kB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 19, 2023