Journal article

Publication year: 2008

Pages: 13244-13248

Journal: The Journal of Physical Chemistry A

Volume number: 112

Issue number: 50

DOI Link: https://doi.org/10.1021/jp803811s

Publisher: American Chemical Society

Abstract: 

The current case study focuses on the generation, identification, and
characterization of two representative mono- and disubstituted alkyl
phosphonatocarbenes by means of matrix isolation techniques in
conjunction with density functional theory [B3LYP/6-311++G(d,p)] and
coupled cluster [CCSD(T)/cc-pVXZ, X = D, T] computations. The EPR
measurements identify both carbenes as triplet ground-state species with
D values of 0.660 and 0.623 cm⁻¹, respectively,
exhibiting persistency toward intramolecular reactions (the EPR signal
observable in perfluoromethylcyclohexane up to around 70 K for the
disubstituted molecule). While the reaction of the carbene center of the
conformationally rich tetramethyl bisphosphonatocarbene with the CH
bonds of the methyl groups leads to phosphaoxetane at room temperature,
its fragmentation via a Wittig-type reaction during high vacuum flash
pyrolysis (HVFP) results in dimethyl vinylphosphonate and methyl
metaphosphate. The latter has been observed for the first time as an
isolated entity.

Harvard Citation style: Nemirowski, A., Reisenauer, H., Romanski, J., Mloston, G. and Schreiner, P. (2008) Prototypical Triplet Alkyl Phosphonatocarbenes, The Journal of Physical Chemistry A, 112(50), pp. 13244-13248. https://doi.org/10.1021/jp803811s

APA Citation style: Nemirowski, A., Reisenauer, H., Romanski, J., Mloston, G., & Schreiner, P. (2008). Prototypical Triplet Alkyl Phosphonatocarbenes. The Journal of Physical Chemistry A. 112(50), 13244-13248. https://doi.org/10.1021/jp803811s