10.1021/om4007278.s002
Katsuhiko Takeuchi
Katsuhiko
Takeuchi
Lindsay J. Hounjet
Lindsay J.
Hounjet
Douglas W. Stephan
Douglas W.
Stephan
Frustrated Lewis Pair Route to Hydrodesilylation of
Silylphosphines
American Chemical Society
2013
H 3P
heptanone
silyl enol ether
mixture
Frustrated Lewis Pair Route
3SiO
3 equiv
2013-08-26 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Frustrated_Lewis_Pair_Route_to_Hydrodesilylation_of_Silylphosphines/2384005
A 1:1 mixture of
P(SiMe<sub>3</sub>)<sub>3</sub> and B(<i>p</i>-C<sub>6</sub>F<sub>4</sub>H)<sub>3</sub> reacts with 3
equiv of 4-heptanone to afford a 1:2 mixture of [(Me<sub>3</sub>SiO)(<i>n</i>-Pr)<sub>2</sub>C]H<sub>2</sub>P–B(<i>p</i>-C<sub>6</sub>F<sub>4</sub>H)<sub>3</sub> and the silyl enol ether,
4-trimethylsiloxy-3-heptene. Subsequent thermolysis of the adduct
produces H<sub>3</sub>P–B(<i>p</i>-C<sub>6</sub>F<sub>4</sub>H)<sub>3</sub> and an additional equiv of silyl enol ether.
In the presence of a catalytic quantity of B(<i>p</i>-C<sub>6</sub>F<sub>4</sub>H)<sub>3</sub>, however, P(SiMe<sub>3</sub>)<sub>3</sub> reacts with 4-heptanone
to produce a 1:1 mixture of [(Me<sub>3</sub>SiO)(<i>n</i>-Pr)<sub>2</sub>C]<sub>2</sub>PH and silyl enol ether. Heating this
mixture further produces [(Me<sub>3</sub>SiO)(<i>n</i>-Pr)<sub>2</sub>C]PH<sub>2</sub>, which is eventually converted to elemental
phosphorus.