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Valence-Bond Concepts in Transition Metals: Metal Hydride Diatomic Cations

Ohanessian, Gilles and Goddard, William A., III (1990) Valence-Bond Concepts in Transition Metals: Metal Hydride Diatomic Cations. Accounts of Chemical Research, 23 (11). pp. 386-392. ISSN 0001-4842. doi:10.1021/ar00179a007.

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Despite the recent advances in understanding bonds between transition metals (TM) and non-metal, there remain considerable uncertainties in both the concepts and the thermodynamics of organometallic complexes, severely limiting the understanding of mechanisms for various chemical transformation. In order to provide the flavor of some of the evolving concepts, we will focus here on MH^+ and examine the variations in bond orbitals, bond energies, and other quantities (from both experiment4 and theory) for the three rows of TM (Sc^+-Cu^+, Y^+-Ag^+, La^+, Hf^+-Au^+) plus the group 2 and group 12 systems. These trends also apply to other bonds to TM, in particular to metal-alkyP and metal-silyl bonds, and should be helpful in estimating and understanding the trends in other TM compounds as well.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1990 American Chemical Society. Received December 4, 1989. Revised Manuscript Received August 3, 1990. Published online 1 May 2002. Our inspiration in using valence bond concepts for transition metals derives from Linus Pauling's classic, Nature of the Chemical Bond. We hope the ideas here show how VB concepts can provide additional qualitative and quantitative understanding of transition-metal systems. The systematic studies on the first two rows of TM hydrides carried out with Dr. J. B. Schilling (now at Amoco Research Center) and Prof. J. L. Beauchamp (Caltech) led to the concepts that form the basis of this review. The similar studies on the third row TM hydrides with M. J. Brusich (now at IDA) are combined here with the earlier ones to provide an overview of MH^+ bonds for all three rows. Some of these concepts go back to the earliest GVB calculations on TM complexes carried out in collaboration with Dr. T. H. Upton (now at Exxon), Dr. C. F. Melius (now at Sandia Livermore Laboratory), Dr. B. D. Olafson (now at BioDesign, Inc.) and M. J. Sollenberger, M.D. (now in private practice). The calculations have been supported by the National Science Foundation (Grant No. CHE-8318041). G.O. is grateful to NATO for a fellowship supporting part of his stay at Caltech. In addition, the computer resources (Alliant FX8l8 and DEC VAX 8650) were funded by ONR/DARPA, NSF-MRG, ONR-SRO, and DOE-ECUT.
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North Atlantic Treaty Organization (NATO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7955
Issue or Number:11
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Official Citation:Valence-bond concepts in transition metals: metal hydride diatomic cations Gilles Ohanessian and William A. Goddard, III Accounts of Chemical Research 1990 23 (11), 386-392 DOI: 10.1021/ar00179a007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85329
Deposited By: Ruth Sustaita
Deposited On:16 Mar 2018 15:16
Last Modified:15 Nov 2021 20:27

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