10.1021/om900944v.s001
Kandasamy Vaheesar
Kandasamy
Vaheesar
Timothy M. Bolton
Timothy M.
Bolton
Allan L. L. East
Allan
L. L. East
Brian T. Sterenberg
Brian T.
Sterenberg
Si−H Bond Activation by Electrophilic Phosphinidene Complexes
American Chemical Society
2010
SiR
silyl phosphine complexes
nucleophilic attack
Electrophilic Phosphinidene ComplexesThe terminal electrophilic phosphinidene
transition state
bond
Si
chloride abstraction
2H
CpFe
2010-01-25 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Si_H_Bond_Activation_by_Electrophilic_Phosphinidene_Complexes/2797696
The terminal electrophilic phosphinidene complex [CpFe(CO)<sub>2</sub>{PN-<i>i</i>-Pr<sub>2</sub>}][AlCl<sub>4</sub>] (<b>2</b>), generated via chloride abstraction from [CpFe(CO)<sub>2</sub>{P(Cl)N-<i>i</i>-Pr<sub>2</sub>}] (<b>1</b>), reacts with primary, secondary, and tertiary silanes to form the silyl phosphine complexes [CpFe(CO)<sub>2</sub>{P(H)(SiR<sub>3</sub>)N-<i>i</i>-Pr<sub>2</sub>}][AlCl<sub>4</sub>] (<b>3</b>, SiR<sub>3</sub> = SiPhH<sub>2</sub>; <b>4</b>, SiR<sub>3</sub> = SiPh<sub>2</sub>H; <b>5</b>, SiR<sub>3</sub> = SiEt<sub>3</sub>), in which the phosphinidene has inserted into the Si−H bond. A computational study shows that the insertion is concerted and has a triangular transition state. The silyl phosphine complexes <b>3</b>, <b>4</b>, and <b>5</b> are very susceptible to nucleophilic attack, which leads to P−Si bond cleavage and formation of the bridging phosphido complex [{CpFe(CO)}<sub>2</sub>(μ-CO){μ-P(H)N<i>-i-</i>Pr<sub>2</sub>}][AlCl<sub>4</sub>] (<b>6</b>).