Phosphinidene complexes [L n M=P À R] [1] are fascinating reagents akin to the isoelectronic carbenes [L n M=CR 2 ] [2] that have made a stunning impact on the preparative and industrial scale syntheses of small molecules and polymeric materials. It is tempting to extend the relationship for lowvalent species that is based on the similar electronegativities of the element phosphorus and the diagonally related carbon to these transition-metal complexes.[3] It has already been established that phosphinidene complexes can be classified as electrophilic (Fischer-type) or nucleophilic (Schrock-type) at phosphorus depending on the nature of the ligands L; [4] electron-withdrawing ligands with strong pacceptor capacity (e.g., CO) reduce the charge concentration on the phosphorus atom and therefore enhance its electrophilicity, whereas strong s-donor ligands (e.g., Cp) increase the electron density at phosphorus and thereby increase its nucleophilic properties. Proper characterisation of these complexes assists in understanding their chemical potential.
Phosphinidene complex [Me3NC6H4PW(CO)5]+ was observed by tandem mass spectrometry and its identity was confirmed by the addition to alkenes in the instrument's ion guide that is shown in the background of the cover picture. The gas‐phase experiments are consistent with solution‐phase and computational studies as reported by K. Lammertsma, P. Chen et al. in their Communication on .
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