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A DFT Study on the Stabilization of the B equivalent to B Triple Bond in a Metallaborocycle: Contrasting Electronic Structures of Boron and Carbon Analogues

Ghorai, Sagar and Jemmis, Eluvathingal D (2017) A DFT Study on the Stabilization of the B equivalent to B Triple Bond in a Metallaborocycle: Contrasting Electronic Structures of Boron and Carbon Analogues. In: CHEMISTRY-A EUROPEAN JOURNAL, 23 (41). pp. 9746-9751.

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Official URL: http://doi.org/10.1002/chem.201702422

Abstract

The electronic structure of (eta(5)-Cp)(2)Zr( NH2-BBNH2) (3b) suggests that it could be a candidate for having a boron-boron triple bond in the cyclic system; however, computational studies shows that 3b is a very high energy isomer on its potential energy surface. Replacement of amines with tricoordinate nucleophilic boron groups (eta(5)-Cp)(2)Zr B(PH3)(2)-BB-B(PH3)(2)] (3c) reduces the relative energy dramatically. The B / B triple bond arises through the donation of two electrons from the metal fragment, ZrCp2, to the in-plane sigma-bonding orbital of the central B-B unit. Strong s-donating and chelating bisphosphine ligands ( Me2P( CH2) nPMe(2)), which stabilize donor-acceptor bonding interaction in gem-diborene L2BBBr2 ( 10), would be a good choice along the synthetic path towards 3d, (eta(5)-Cp)(2)ZrB-4(Me2P(CH2)(3)PMe2)(2)]. A comparison of the energetics of the reaction leading to a cyclic boryne system (3d), with the linear boryne isomer (B2NHCPh)(2)] shows that the angle strain from cyclization is compensated by stabilization from the metal.

Item Type: Journal Article
Additional Information: Copy right for this article belongs to the WILEY-V C H VERLAG GMBH, POSTFACH 101161, 69451 WEINHEIM, GERMANY
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 16 Aug 2017 06:33
Last Modified: 16 Aug 2017 06:33
URI: http://eprints.iisc.ac.in/id/eprint/57642

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