Even the normal is abnormal: N-heterocyclic carbene C 2 binding to a phosphaalkene without breaking the P-C π-bond

Even the normal is abnormal: N-heterocyclic carbene C 2 binding to a phosphaalkene without breaking the P-C π-bond. Majhi, P., K., Chow, K., C., F., Hsieh, T., H., H., Bowes, E., G., Schnakenburg, G., Kennepohl, P., Streubel, R., & Gates, D., P. Chem. Commun., 52(5):998-1001, 2016.

Paper

Even the normal is abnormal: N-heterocyclic carbene C 2 binding to a phosphaalkene without breaking the P-C π-bond [link]

Website doi abstract bibtex

The reaction of MesPQCPh2 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)QCPh2 (2). Particularly striking is the asymmetric and weak bonding of the NHC to the PQC moiety in 2. DFT calculations indicate that the PQC natural bond order in 2 (1.54) still reflects significant pi-character to the bond (cf. MesPQCPh2: NBO = 1.98). Further computational analysis suggests that p-delocalization into the remote C-phenyl substituents is key to stabilizing the NHC adduct.

@article{
 title = {Even the normal is abnormal: N-heterocyclic carbene C 2 binding to a phosphaalkene without breaking the P-C π-bond},
 type = {article},
 year = {2016},
 keywords = {Westgrid},
 pages = {998-1001},
 volume = {52},
 websites = {http://xlink.rsc.org/?DOI=C5CC08181E},
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 created = {2017-09-06T15:15:18.706Z},
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 last_modified = {2017-09-06T15:32:08.166Z},
 read = {true},
 starred = {false},
 authored = {true},
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 abstract = {The reaction of MesPQCPh2 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)QCPh2 (2). Particularly striking is the asymmetric and weak bonding of the NHC to the PQC moiety in 2. DFT calculations indicate that the PQC natural bond order in 2 (1.54) still reflects significant pi-character to the bond (cf. MesPQCPh2: NBO = 1.98). Further computational analysis suggests that p-delocalization into the remote C-phenyl substituents is key to stabilizing the NHC adduct.},
 bibtype = {article},
 author = {Majhi, Paresh Kumar and Chow, Keith C F and Hsieh, Tom H H and Bowes, Eric G and Schnakenburg, Gregor and Kennepohl, Pierre and Streubel, Rainer and Gates, Derek P},
 doi = {10.1039/C5CC08181E},
 journal = {Chem. Commun.},
 number = {5}
}

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