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

Bathie, F, Stewart, A, Canty, AJ and O'Hair, RAJ 2021 , 'Dissecting transmetalation reactions at the molecular level: C-B versus F-B bond activation in phenyltrifluoroborate silver complexes' , Dalton Transactions, vol. 50, no. 4 , pp. 1496-1506 , doi: 10.1039/d0dt03309j.

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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 Type: Article
Authors/Creators:Bathie, F and Stewart, A and Canty, AJ and O'Hair, RAJ
Keywords: silver, transmetalation, mass spectrometry, computation, DFT
Journal or Publication Title: Dalton Transactions
Publisher: Royal Soc Chemistry
ISSN: 1477-9226
DOI / ID Number: 10.1039/d0dt03309j
Copyright Information:

© The Royal Society of Chemistry 2021

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