Olefin Cycloadditions of the Electrophilic Phosphinidene Complex [iPr2N−P=Fe(CO)4]

Abstract

Highly strained methylenephosphiranes are formed in the reaction of the new electrophilic phosphinidene complex [iPr(2)N-P=Fe(CO)(4)] with allenes. Remarkably, reaction with diallenes at 0 degrees C also leads to a phosphirane, which rearranges upon warming to room temperature to a bis-isopropylidenephospholene (see scheme).

Carbene-Like Chemistry of Phosphinidene Complexes − Reactions, Applications, and Mechanistic Insights

“…A similar reactivity pattern has been reported for the reaction between an iron‐complexed phosphinidene and diallene 51 38a. Ab initio calculations showed that reaction at a conjugated double bond is favored by 6 kcal·mol −1 over reaction at a terminal one.…”

Phosphaorganische Chemie: Panorama und Perspektiven

“…Tabelle 1 fasst die Ergebnisse einer DFT‐Studie zusammen 137. Damit erklärt sich auch die Elektrophilie der Phosphinideneinheit in [ i Pr 2 NPFe(CO) 4 ]:146 Der Aminosubstituent am P‐Zentrum hat π‐Donoreigenschaften und induziert so die Polarisierung der PFe‐Bindung. Bei den von Carty et al beschriebenen elektrophilen Komplexen (z.…”

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

“…Finally, a [Fe(phosphinidene)(CO) 4 ] complex, prepared as shown in Eqn. 4, has been condensed with allenes and diallenes [44] (Eqn. 22).…”