Dinuclear metalloradicals featuring unsupported metal-metal bonds

Edwin F. Van Der Eide; Ping Yang; Eric D. Walter; Tianbiao Liu; R. Morris Bullock

doi:10.1002/anie.201203531

Dinuclear metalloradicals featuring unsupported metal-metal bonds

Edwin F. Van Der Eide, Ping Yang, Eric D. Walter, Tianbiao Liu, R. Morris Bullock

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

Abstract

No support required: Unlike the unobservable radical cations [{CpM(CO) ₃}₂]^.+ (M=W, Mo), derivatives [{CpM(CO) ₂(PMe₃)}₂]^.+ are stable enough to be isolated and characterized. Experimental and theoretical studies show that the shortened M-M bonds are of order 1 1/2, and that they are not supported by bridging ligands. The unpaired electron is delocalized over the M-M cores, with a spin density of about 45 % on each metal atom.

Original language	English
Pages (from-to)	8361-8364
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	51
Issue number	33
DOIs	https://doi.org/10.1002/anie.201203531
Publication status	Published - Aug 13 2012

Keywords

EPR spectroscopy
density functional calculations
metalloradicals
mixed-valent dimers
redox chemistry

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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title = "Dinuclear metalloradicals featuring unsupported metal-metal bonds",

abstract = "No support required: Unlike the unobservable radical cations [{CpM(CO) 3}2].+ (M=W, Mo), derivatives [{CpM(CO) 2(PMe3)}2].+ are stable enough to be isolated and characterized. Experimental and theoretical studies show that the shortened M-M bonds are of order 1 1/2, and that they are not supported by bridging ligands. The unpaired electron is delocalized over the M-M cores, with a spin density of about 45 % on each metal atom.",

keywords = "EPR spectroscopy, density functional calculations, metalloradicals, mixed-valent dimers, redox chemistry",

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T1 - Dinuclear metalloradicals featuring unsupported metal-metal bonds

AU - Van Der Eide, Edwin F.

AU - Yang, Ping

AU - Walter, Eric D.

AU - Liu, Tianbiao

AU - Bullock, R. Morris

PY - 2012/8/13

Y1 - 2012/8/13

N2 - No support required: Unlike the unobservable radical cations [{CpM(CO) 3}2].+ (M=W, Mo), derivatives [{CpM(CO) 2(PMe3)}2].+ are stable enough to be isolated and characterized. Experimental and theoretical studies show that the shortened M-M bonds are of order 1 1/2, and that they are not supported by bridging ligands. The unpaired electron is delocalized over the M-M cores, with a spin density of about 45 % on each metal atom.

AB - No support required: Unlike the unobservable radical cations [{CpM(CO) 3}2].+ (M=W, Mo), derivatives [{CpM(CO) 2(PMe3)}2].+ are stable enough to be isolated and characterized. Experimental and theoretical studies show that the shortened M-M bonds are of order 1 1/2, and that they are not supported by bridging ligands. The unpaired electron is delocalized over the M-M cores, with a spin density of about 45 % on each metal atom.

KW - EPR spectroscopy

KW - density functional calculations

KW - metalloradicals

KW - mixed-valent dimers

KW - redox chemistry

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