Effective core potential study of multiply bonded transition metal complexes of the heavier main group elements

A computational study, using relativistic effective core potentials, is presented of transition metalmain group multiply bonded complexes, of interest in the context of catalysis and chemical vapor deposition of TM/MG materials. Model d⁰ transition metal complexes chosen are of the general form Cl_nME 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 Møller–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. To date no examples have been reported of arsinidene and stibinidene complexes. Computational results show similar behavior among the heavier pnictogen complexes, i.e., L_nM  EH (E = P, As, Sb), suggesting that strategies used to synthesize phosphinidenes may be suitable in the search for the first L_nM  AsR and L_nM  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. © 1994 John Wiley & Sons, Inc.