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Dinuclear Metalloradicals Featuring Unsupported Metal–Metal Bonds

Authors

  • Dr. Edwin F. van der Eide,

    1. Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
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  • Dr. Ping Yang,

    Corresponding author
    1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
    • Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
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  • Dr. Eric D. Walter,

    1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
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  • Dr. Tianbiao Liu,

    1. Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
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  • Dr. R. Morris Bullock

    Corresponding author
    1. Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
    • Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA)
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  • We thank the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support of this work. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The EPR and computational studies were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. We thank Dr. Aaron Appel for useful discussions, and Dr. Charles Windisch for access to his UV/Vis/NIR spectrometer.

Abstract

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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[BOND]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[BOND]M cores, with a spin density of about 45 % on each metal atom.

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