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Volumn 48, Issue 16, 2009, Pages 7794-7799

Copper corroles are inherently saddled

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EID: 68949147556     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic900744v     Document Type: Article
Times cited : (106)

References (59)
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    • The DFT (OLYP) calculations were carried out with the ADF2007 program system using the methods described in: Velde, G. T.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C. F.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931-967.
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    • The ADF program system was obtained from Scientific Computing and Modeling, Amsterdam, The Netherlands (http://www.scm.com/). For a description of the methods used in ADF, see: Velde, G. T.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C. F.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931-967.
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    • The situation is quite different for middle-transition-metal porphyrins, notably hemes, where different functionals often give widely divergent results. For a relevant recent study on nickel hydroporphyrins, see
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    • Given that copper corroles are four-coordinate and Co IIIPPh3 corroles are five-coordinate, the question might be raised as to whether PPh3 exerts a planarizing influence in the latter case. To address this question, we also calculated the saddling potentials for four-coordinate cobalt(III) corroles. For unsubstituted corrole and TPC, Χ < 10° for both the S, 0 and 1 spin states of the four-coordinate cobalt(III) complex. Even for CoIIIBr 8TPC, the saddling dihedral was found to be only about 16°. Thus, the triphenylphosphine ligand does not play a significant role in conferring a planar geometry on cobalt corroles
    • 8TPC), the saddling dihedral was found to be only about 16°. Thus, the triphenylphosphine ligand does not play a significant role in conferring a planar geometry on cobalt corroles.
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