The nature of M-B versus M=B bonds in cationic terminal borylene complexes: Structure and energy analysis in the borylene complexes [(η<sup>5</sup>- C<inf>5</inf>H<inf>5</inf>)(CO)<inf>2</inf>M{B(η<sup>5</sup>-C <inf>5</inf>Me<inf>5</inf>)}]<sup>+</sup>, [(η<sup>5</sup>-C <inf>5</inf>H<inf>5</inf>)(CO)<inf>2</inf>M(BMeS)]<sup>+</sup>, and [(η<sup>5</sup>-C<inf>5</inf>H<inf>5</inf>)

Krishna K. Pandey, Agustí Lledós, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

18 Citations (Scopus)

Abstract

Density functional theory calculations have been performed for the terminal cationic borylene complexes [(η5-C5H 5)(CO)2M {B(η5-C5Me 5)}]+, [(η5-C5H 5)(CO)2M(BMes)]+, and [(η5- C5H5)(CO)2M(BNMe2)]+ (M = Fe, Ru, Os) using the exchange correlation functional BP86. The optimized bond lengths and angles of the complexes are in excellent agreement with experiment. The M-B bond distances in the complexes [(η5-C5H 5)(CO)2M{B(η5-C5Me 5)}]+ (I, M = Fe; II, M = Ru; III, M = Os) are similar to those expected for single bonds on the basis of covalent radii predictions. In contrast, the optimized M-B bond distances in the complexes [(η5- C5H5)(CO)2M(BMes)]+ and [(η5-C5H5)(CO)2M(BNMe 2)]+ correspond to a Pauling bond order of 1.73-1.42. The contribution of the electrostatic interaction ΔEelstat is significantly larger in all borylene complexes than the covalent bonding ΔEorb, the [M]-BR bonding in the cationic borylene complexes having a greater degree of ionic (60.6-66.8%) than covalent character. The orbital interactions between metal and boron in [(η5-C 5H5)(CO)2M{B(η5-C 5Me5)}]+, [(η5-C 5H5)(CO)2M(BMes)]+, and [(η5-C5H5)(CO)2Fe(BNMe 2)]+ arise mainly from M-BR σ donation. The π-bonding contribution is, in all complexes, much smaller (9.0-17.3% of total orbital contributions). © 2009 American Chemical Society.
Original languageEnglish
Pages (from-to)6442-6449
JournalOrganometallics
Volume28
Issue number22
DOIs
Publication statusPublished - 23 Nov 2009

Fingerprint Dive into the research topics of 'The nature of M-B versus M=B bonds in cationic terminal borylene complexes: Structure and energy analysis in the borylene complexes [(η<sup>5</sup>- C<inf>5</inf>H<inf>5</inf>)(CO)<inf>2</inf>M{B(η<sup>5</sup>-C <inf>5</inf>Me<inf>5</inf>)}]<sup>+</sup>, [(η<sup>5</sup>-C <inf>5</inf>H<inf>5</inf>)(CO)<inf>2</inf>M(BMeS)]<sup>+</sup>, and [(η<sup>5</sup>-C<inf>5</inf>H<inf>5</inf>)'. Together they form a unique fingerprint.

Cite this