Effective core potential study of multiply bonded transition metal complexes of the heavier main group elements
- Memphis State Univ., TN (United States); and others
A computational study, using relativistic effective core potentials, is presented of transition metal-main group multiply bonded complexes, of interest in the context of catalysis and chemical vapor deposition of TM/MG materials. Model d{sup 0} transition metal complexes chosen are of the general form C1{sub n}ME where M = Zr (n = 2), Ta (n = 3), and W (n = 4). Main group elements of interest are the tetrels (E = C, Si, Ge, Sn), pnictogens (E = N, P, As, Sb), and chalcogens (E = O, S, Se, Te). A comparison between calculated metric data and available experimental data for a wide range of TM=MG complexes will help in further assessing efficient computational approaches to TM complexes, particularly of the heavier MG elements, as a function of metal, ligand and level of theory. In the present work, restricted Hartree Fock (RHF) and Moeller-Plesset second order perturbation theory (MP2) wavefunctions were employed. In most cases there are small differences between RHF and MP2 calculated geometries with both methods showing good agreement with experimental data, suggesting these approaches will be suitable for the study of larger, more experimentally relevant models. Changes in ZrE bond lengths for E = chalcogen (upon going from RHF to MP2) suggest a fundamentally different description between the Zr-oxo bond and heavier chalcogens, a result supported by recent experimental data for a series of Zr-chalcogenidos. Computational results show similar behavior among the heavier pnictogen complexes, i.e., L{sub n}M=EH(E=P, As, Sb), suggesting that strategies used to synthesize phosphinidenes may be suitable in; the search for the first L{sub n}M=AsR and L{sub n}M=SbR complexes. Additionally, calculations suggest that design of ligand sets which yield linearly coordinated phosphinidenes (and presumably As and Sb analogues) will lead to phosphinidenes with stronger metal-pnictogen bonds and increased thermodynamic stability versus nonlinearly coordinated examples.
- OSTI ID:
- 107042
- Report Number(s):
- CONF-9402143-; CNN: Grant CHE-9314732; TRN: 95:006488-0016
- Resource Relation:
- Conference: Atomic, molecular, and condensed matter theory and computational methods, Ponte Vedra Beach, FL (United States), 12-19 Feb 1994; Other Information: PBD: 1994; Related Information: Is Part Of Proceedings of the international symposium on atomic, molecular and condensed matter theory and computational methods; Loewdin, P.O.; Oehrn, N.Y.; Sabin, J.R.; Zerner, M.C. [eds.] [Florida Univ., Gainesville, FL (United States)]; PB: 714 p.
- Country of Publication:
- United States
- Language:
- English
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