ISSN:
0947-6539
Keywords:
ab initio calculations
;
copper compounds
;
organometallic compounds
;
tetrahydroborato ligand
;
theoretical chemistry
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
All-electron ab initio calculations (MP4/MP2 level) have been performed on [Cu(BH4)(PH3)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 η2 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 η1 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 η3 structure turns out to be the most stable. The energy differences associated with some changes in the coordination mode (η1 → η2 for n = 3 and η3 → η2 for n = 1) are small. Finally, a mechanism for the exchange between terminal and bridging hydrogen atoms is proposed for each complex under study.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19950010708
Permalink
