Article ; Online: Even the normal is abnormal: N-heterocyclic carbene C(2) binding to a phosphaalkene without breaking the P=C π-bond.
Chemical communications (Cambridge, England)
2016 Volume 52, Issue 5, Page(s) 998–1001
Abstract: ... with Me2IMe gives the unprecedented 'normal' C(2) adduct, Me2IMe → P(Mes)=CPh2 (2). Particularly striking is ... the asymmetric and weak bonding of the NHC to the P=C moiety in 2. DFT calculations indicate that the P=C natural ... results in formation of the 'abnormal' (C(4)-substituted) 4-phosphino-NHC (1). In contrast, reaction ...
Abstract | The reaction of MesP=CPh2 with the least sterically demanding N-heterocyclic carbene (NHC = IMe) results in formation of the 'abnormal' (C(4)-substituted) 4-phosphino-NHC (1). In contrast, reaction with Me2IMe gives the unprecedented 'normal' C(2) adduct, Me2IMe → P(Mes)=CPh2 (2). Particularly striking is the asymmetric and weak bonding of the NHC to the P=C moiety in 2. DFT calculations indicate that the P=C natural bond order in 2 (1.54) still reflects significant π-character to the bond (cf. MesP=CPh2: NBO = 1.98). Further computational analysis suggests that π-delocalization into the remote C-phenyl substituents is key to stabilizing the NHC adduct. |
---|---|
Language | English |
Publishing date | 2016-01-18 |
Publishing country | England |
Document type | Journal Article ; Research Support, Non-U.S. Gov't |
ZDB-ID | 1472881-3 |
ISSN | 1364-548X ; 1359-7345 ; 0009-241X |
ISSN (online) | 1364-548X |
ISSN | 1359-7345 ; 0009-241X |
DOI | 10.1039/c5cc08181e |
Database | MEDical Literature Analysis and Retrieval System OnLINE |
More links
Kategorien
Order via subito
This service is chargeable due to the Delivery terms set by subito. Orders including an article and supplementary material will be classified as separate orders. In these cases, fees will be demanded for each order.