Reactions of Li/Cl Phosphinidenoid Complexes with 1,3,4,5‐Tetramethylimidazol‐2‐ylidene: A New Route to N‐Heterocyclic Carbene Adducts of Terminal Phosphin­idene Complexes and an Unprecedented Transformation of an Oxaphosphirane Complex

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<jats:title>Abstract</jats:title><jats:p>The reaction of Li/Cl phosphinidenoid tungsten(0) complex <jats:bold>2</jats:bold> [R = CH(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] with 1,3,4,5‐tetramethylimidazol‐2‐ylidene (<jats:bold>3</jats:bold>) yielded the zwitterionic phosphaalkene complex <jats:bold>4</jats:bold>. A comparative study on chloro‐ (<jats:bold>5</jats:bold>) or dichloro(organo)phosphane complexes <jats:bold>1</jats:bold> [R = CH(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] and NHC <jats:bold>3</jats:bold> revealed the formation of <jats:bold>4</jats:bold> at ambient temperature. First evidence for the formation of phosphinidenoid complex <jats:bold>7</jats:bold>, having a <jats:italic>C</jats:italic>‐Cl imidazolium cation, and its reaction with benzaldehyde to give oxaphosphirane complex <jats:bold>9</jats:bold> are presented. Furthermore, the first example of a formal exchange at the phosphorus center of an oxaphosphirane complex to give zwitterion <jats:bold>4</jats:bold> is demonstrated.</jats:p>

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