NDLI: What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [ (H) $_{2}Cl(PMe$ $_{3})$ $

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Pandey, Krishna K.
Description	Author Affiliation: Pandey KK ( School of Chemical Sciences, Devi Ahilya University Indore, Indore, India. kkpandey.schem@dauniv.ac.in)
Abstract	Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron , ruthenium and osmium [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}M(σ-H-BR)$ ] (M = Fe , Ru , Os; R = OMe , NMe $_{2}$ , Ph) at the BP86 / TZ2P / ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}Ru(HBNMe$ $_{2})$ ], [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}Os(HBR)$ ] (R = OMe , NMe $_{2}$ ) are in excellent agreement with structurally characterized complexes [ (H) $_{2}Cl(P$ $^{i}Pr$ $_{3})$ $_{2}Os(σ-H-BNMe$ $_{2})$ ], [ (H) $_{2}Cl(P$ $^{i}Pr$ $_{3})$ $_{2}Os\{σ-H-BOCH$ $_{2}CH$ $_{2}OB(O$ $_{2}CH$ $_{2}CH$ $_{2})\}$ ] and [(H) $_{2}Cl(P$ $^{i}Pr$ $_{3})$ $_{2}Os(σ-H-BNMe$ $_{2})]$ . The longer calculated M–B bond distance in complex [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}M(σ-H-BNMe$ $_{2})$ ] are due to greater B–N π bonding and as a result, a weaker M–B π-back-bonding. The B–H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B–H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M–(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M–σ-H-BR interactions in the complexes [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}M(σ-H-BR)$ ] is the interaction between neutral fragments [ (H) $_{2}Cl(PMe$ $_{3})$ $_{2}M$ ] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M–σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the $ΔE_{prep}$ values, it is clearly the most appropriate choice of interacting fragments. The π-bonding contribution is 14–22% of the total orbital contribution.
ISSN	14779226
Issue Number	11
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-03-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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