Unexpected Migratory Insertion Reactions of M(alkyl)2 (M = Zn, Cd) and Diamidocarbenes

Lee Collins, Gabriele Hierlmeier, Mary Mahon, Ian Riddlestone, Michael Whittlesey

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Abstract

The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6-MesDAC-R)MR] (M = Zn, Cd; R = Et, Me; Mes = mesityl). These species were formed via the spectroscopically characterised intermediates, [(6-MesDAC)MR2], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2. Compound [(6-MesDAC-Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent beta-H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M-R, M-H).
Original languageEnglish
Pages (from-to)3215-3218
Number of pages4
JournalChemistry - A European Journal
Volume21
Issue number8
Early online date8 Jan 2015
DOIs
Publication statusPublished - Feb 2015

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Unexpected Migratory Insertion Reactions of M(alkyl)2 (M = Zn, Cd) and Diamidocarbenes. / Collins, Lee; Hierlmeier, Gabriele; Mahon, Mary; Riddlestone, Ian; Whittlesey, Michael.

In: Chemistry - A European Journal, Vol. 21, No. 8, 02.2015, p. 3215-3218.

Research output: Contribution to journalArticle

Collins, Lee ; Hierlmeier, Gabriele ; Mahon, Mary ; Riddlestone, Ian ; Whittlesey, Michael. / Unexpected Migratory Insertion Reactions of M(alkyl)2 (M = Zn, Cd) and Diamidocarbenes. In: Chemistry - A European Journal. 2015 ; Vol. 21, No. 8. pp. 3215-3218.
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