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B-B Coupling and B-B Catenation: Computational Study of the Structure and Reactions of Metal-Bis(borylene) Complexes

Ghorai, Sagar and Jemmis, Eluvathingal D (2018) B-B Coupling and B-B Catenation: Computational Study of the Structure and Reactions of Metal-Bis(borylene) Complexes. In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (67). pp. 17844-17851.

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Official URL: https://doi.org/ 10.1002/chem.201804599

Abstract

A detailed molecular orbital analysis of the metal-bis(borylene) complex Fe(CO)(3){B(Dur)B(N(SiMe3)(2))}] (Dur=2,3,5,6-tetramethylphenyl) (1 a) serves as a focal point of recent developments in this area of chemistry, such as B-B coupling and B-B catenation reactions. There is strong a pi delocalization between the Fe(CO)(3) and (B-Dur)(B-N(SiMe3)(2)) units; the short B-B distance in 1 a is due to this pi delocalization. The pi-donor ligand N(SiMe3)(2) on the boron provides a decisive stability to the complex 1 a. The LUMO of 1 a has B-B sigma-bonding character. Hence B-B coupling is facilitated by filling the LUMO. Strong sigma-donating ligands, such as PMe3 or PCy3, induce B-B coupling. Expulsion of one CO from 1 a followed by dimerization leads to Fe(CO)(2){B(Dur)B(N(SiMe3)(2))}](2) (3 a) with a short Fe-Fe distance of 2.355 angstrom. A detailed mechanism for the reaction of 3 a with CO to give the B-B catenation product 2 f is presented. The bonding of all intermediates is compared to their isolobal main-group analogues.

Item Type: Journal Article
Additional Information: Copyright of this article belong to WILEY-V C H VERLAG GMBH
Keywords: aromaticity; boron; catenanes; isolobal relationship; metal-bis(borylene)
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Francis Jayakanth
Date Deposited: 08 Feb 2019 10:20
Last Modified: 08 Feb 2019 10:20
URI: http://eprints.iisc.ac.in/id/eprint/61364

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