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>).