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Issue 5, 2016
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Even the normal is abnormal: N-heterocyclic carbene C2 binding to a phosphaalkene without breaking the P[double bond, length as m-dash]C π-bond

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Abstract

The reaction of MesP[double bond, length as m-dash]CPh2 with the least sterically demanding N-heterocyclic carbene (NHC = IMe) results in formation of the ‘abnormal’ (C4-substituted) 4-phosphino-NHC (1). In contrast, reaction with Me2IMe gives the unprecedented ‘normal’ C2 adduct, Me2IMe → P(Mes)[double bond, length as m-dash]CPh2 (2). Particularly striking is the asymmetric and weak bonding of the NHC to the P[double bond, length as m-dash]C moiety in 2. DFT calculations indicate that the P[double bond, length as m-dash]C natural bond order in 2 (1.54) still reflects significant π-character to the bond (cf. MesP[double bond, length as m-dash]CPh2: NBO = 1.98). Further computational analysis suggests that π-delocalization into the remote C-phenyl substituents is key to stabilizing the NHC adduct.

Graphical abstract: Even the normal is abnormal: N-heterocyclic carbene C2 binding to a phosphaalkene without breaking the P [[double bond, length as m-dash]] C π-bond

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Supplementary files

Article information


Submitted
02 Oct 2015
Accepted
16 Nov 2015
First published
23 Nov 2015

Chem. Commun., 2016,52, 998-1001
Article type
Communication
Author version available

Even the normal is abnormal: N-heterocyclic carbene C2 binding to a phosphaalkene without breaking the P[double bond, length as m-dash]C π-bond

P. K. Majhi, K. C. F. Chow, T. H. H. Hsieh, E. G. Bowes, G. Schnakenburg, P. Kennepohl, R. Streubel and D. P. Gates, Chem. Commun., 2016, 52, 998
DOI: 10.1039/C5CC08181E

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