A delicate electronic balance between metal and ligand in [Cu-P-Cu-P] diamondoids: Oxidation state dependent plasticity and the formation of a singlet diradicaloid

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Transition metal atoms often participate in redox reactions as catalytic sites, where ligand groups play an important role in orchestrating catalytic activity, especially in metalloenzymes. A major issue is to understand connections between oxidation state and geometry at the metal center, because geometric reorganization is directly related to reaction rate. In this article, we analyze an intriguing oxidation-induced geometrical change in [Cu-P-Cu-P] ring structures (similar to 0.6 angstrom change in metal-metal distance) using quantum chemical approaches. We find that the Cu-P interactions in the ring of the neutral species consist of four localized P --> Cu dative bonds. Successive oxidations extract electrons predominantly from P atoms on the ring rather than Cu sites. It emerges that as a result, the Cu-P interactions change and also exhibit partial Cu(3d) --> P donation, which causes the large distortion in geometry. We also find that the dication possesses a large degree of diradical character, forming a rare example of an observed species that is a singlet diradicaloid. This hypothesis is supported by our computational results as well as previously reported experimental features.
Publisher
AMER CHEMICAL SOC
Issue Date
2008-03
Language
English
Article Type
Article
Keywords

BLUE-COPPER PROTEINS; RAY-ABSORPTION SPECTROSCOPY; ALCALIGENES-FAECALIS S-6; AUXILIARY BASIS-SETS; GAUSSIAN-BASIS SETS; WAVE-FUNCTIONS; MOLECULAR CALCULATIONS; ANGSTROM RESOLUTION; THEORETICAL-MODELS; CRYSTAL-STRUCTURE

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.130, no.12, pp.3878 - 3887

ISSN
0002-7863
DOI
10.1021/ja0764916
URI
http://hdl.handle.net/10203/225408
Appears in Collection
CH-Journal Papers(저널논문)
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