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Ab initio Study of the Coordination Modes of the Tetrahydroborato Ligand: Structure of the [Cu(BH 4 )(PH 3 ) n ] ( n = 1, 2, 3) Complexes
Author(s) -
Jarid A.,
Lledos A.,
Jean Y.,
Volatron F.
Publication year - 1995
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19950010708
Subject(s) - ab initio , chemistry , crystallography , tetrahedron , ab initio quantum chemistry methods , atom (system on chip) , hessian matrix , coordination number , coordination geometry , computational chemistry , hydrogen bond , molecule , ion , mathematics , organic chemistry , computer science , embedded system
Abstract All‐electron ab initio calculations (MP4/MP2 level) have been performed on [Cu(BH 4 )(PH 3 ) n ] ( n = 1, 2, 3) complexes. Full‐geometry optimizations were carried out in each case, and the stationary points were characterized by the diagonalization of the analytically calculated Hessian matrix. The η 2 coordination mode, with a tetrahedral arrangement around the copper atom, is the most stable structure for n = 2, while for n = 3 a strongly nonlinear η 1 coordination mode is preferred. These results are in agreement with the experimental data available on related complexes. For n = 1, for which there is no experimental data, the η 3 structure turns out to be the most stable. The energy differences associated with some changes in the coordination mode (η 1 → η 2 for n = 3 and η 3 → η 2 for n = 1) are small. Finally, a mechanism for the exchange between terminal and bridging hydrogen atoms is proposed for each complex under study.