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Dissecting transmetalation reactions at the molecular level: C-B versus F-B bond activation in phenyltrifluoroborate silver complexes

Citation

Bathie, F and Stewart, A and Canty, AJ and O'Hair, RAJ, Dissecting transmetalation reactions at the molecular level: C-B versus F-B bond activation in phenyltrifluoroborate silver complexes, Dalton Transactions, 50, (4) pp. 1496-1506. ISSN 1477-9226 (2021) [Refereed Article]

Copyright Statement

The Royal Society of Chemistry 2021

DOI: doi:10.1039/d0dt03309j

Abstract

The gas-phase unimolecular reactions of the silver(I) complex [Ag(PhBF3)2], formed via electrospray ionisation mass spectrometry of solutions containing the phenyltrifluoroborate salt and AgNO3, are examined. Upon collision induced dissociation (CID) three major reaction channels were observed for [Ag(PhBF3)2]: Ph group transfer via a transmetalation reaction to yield [PhAg(PhBF3)]; F transfer to produce [FAg(PhBF3)]; and release of PhBF3. The anionic silver product complexes of these reactions, [LAg(PhBF3)] (where L = Ph and F), were then mass-selected and subjected to a further stage of CID. [PhAg(PhBF3)] undergoes a Ph group transfer via transmetalation to yield [Ph2Ag] with loss of BF3. [FAg(PhBF3)] solely fragments via loss of BF4, a reaction that involves Ph group transfer from B to Ag in conjunction with F transfer from Ag to B. Density functional theory (DFT) calculations on the various competing pathways reveal that: (i) the overall endothermicities govern the experimentally observed product ion abundances; (ii) the Ph group and F transfer reactions proceed via late transition states; and (iii) formation of BF4 from [FAg(PhBF3)] is a multistep reaction in which Ph group transfer from B to Ag proceeds first to produce a [FAgPh(BF3)] complex in which the BF3 moiety is initially weakly bound to the ipso-carbon of the phenyl group and then migrates across the linear [FAgPh] moiety from C to Ag to F yielding [PhAg(BF4)], which can then dissociate via loss of PhAg.

Item Details

Item Type:Refereed Article
Keywords:silver, transmetalation, mass spectrometry, computation, DFT
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:144062
Year Published:2021
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2021-04-17
Last Modified:2021-05-04
Downloads:0

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