Valence-Bond Concepts in Transition Metals: Metal Hydride Diatomic Cations
Abstract
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.
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.Additional details
- Eprint ID
- 85329
- DOI
- 10.1021/ar00179a007
- Resolver ID
- CaltechAUTHORS:20180315-104849048
- CHE-8318041
- NSF
- North Atlantic Treaty Organization (NATO)
- Office of Naval Research (ONR)
- Defense Advanced Research Projects Agency (DARPA)
- Department of Energy (DOE)
- Created
-
2018-03-16Created from EPrint's datestamp field
- Updated
-
2021-11-15Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 7955