Bonding studies of derivatives of pentaborane(9) through self-consistent charge calculations
- 1 January 1980
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1236-1242
- https://doi.org/10.1039/dt9800001236
Abstract
Derivatives of pentaborane(9) have been studied by self-consistent charge calculations to examine multicentre bonding and the application of the ‘isolobal, pseudo-isoelectronic’ principles. The results reproduce previously reported photoelectron spectra reasonably well. Interpretation of the results suggests that the differences encountered in bonding apical and basal units are similar for BH, Fe(CO)3, and Co(η5-C5H5) groups. The highest occupied molecular orbitals of B4H9 involve apical boron 2p orbitals and correlate well with cluster orbitals in 1-[B4H8Fe(CO)3] and 1-[B4H8Co(η5-C5H5)] which largely involve metal 3d orbitals. However the next cluster orbital in B5H9 has no direct counterpart in the metal derivatives. The metallo-units appear to be bonded into the cluster by a one-electron, two-orbital combination rather than the two-electron, three-orbital method used by BH. Similarly for the 2-isomers. Replacement of a bridging hydrogen by a µ-(SiH3) unit leaves the cluster substantially unaltered. However with a µ-[Cu(PH3)2] bridging unit the major bonding contribution combines boron s and p and a copper 4p orbital in an ‘open’ three-centre bond.Keywords
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