Marius Papendick, Nicholas Birchall, Martin Nieger and Dietrich Gudat*,
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Isolable N-heterocyclic phosphenium (NHP) complexes of vanadium were prepared by cophotolysis of Na[V(CO)6] and 2-bromo-1,3,2-diazaphospholenes. Single-crystal XRD studies revealed that the complexes exhibit trigonal planar coordination at phosphorus and short P–V distances indicative of phosphorus–metal double bonding. An exemplary reaction with Li[BEt3H] proceeded via hydride transfer to the phosphorus atom to yield an anionic secondary phosphine complex, which resisted protonation by [Et3NH]Cl and differed in this aspect from a previously reported manganese-based analogue. DFT calculations were carried out to analyze metal–ligand interactions in the NHP vanadium complexes and to rationalize the different behavior of the vanadium- and manganese-based species in H–/H+-transfer reactions.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.