Ab initio Study of the Coordination Modes of the Tetrahydroborato Ligand: Structure of the [Cu(BH4)(PH3)n] (n = 1, 2, 3) Complexes

✍ Scribed by A. Jarid; A. Lledos; Y. Jean; F. Volatron

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 432 KB
• Volume: 1
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.19950010708

✦ Synopsis

All-electron ab iiiitio calculations (MP4/MP2 level) have been performed on [Cu(BH,)(PH,),] (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 q2 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 q' coordination mode is preferred. These results are in agreement with the experimental data Keywords ab initio calculations copper cornpounds * organometallic compoundstetrahydroborato tigand theoretical chemistry available on related complexes. For n = 1, for which there is no experimental data, the q3 structure turns out to be the most stable. The energy differences associated with some changes in the coordination mode (q' + q2 for I I = 3 and q3 + q z for n = 1) are small. Finally, a mechanism for the exchange between terminal and bridging hydrogen atoms is proposed for each complex under study.