Phosphinidene

In chemistry phosphinidenes (IUPAC: phosphanylidenes, or in older chemistry phosphinediyls) are the phosphorus analogs of carbenes and nitrenes, having the general structure RP:.[1] The name originated from the parent compound, phosphinidene (HP).[2] They can exist in either a singlet state or triplet state, with the triplet state being lower in energy. This type of compound is very reactive. In 2016, the first isolable singlet phosphinidene (DOI: 10.1016/j.chempr.2016.04.001) has been achieved by Guy Bertrand in University of California, San Diego.

Terminal transition-metal-complexed phosphinidenes LnM=P-R are phosphorus analogs of transition metal carbene complexes where L is a spectator ligand. Two examples of this group are [(OC)5W=P-Ph][3] and Cp2W=P-Mes*.[4]

In clusters

More common than complexes of terminal phosphinidine ligands are cluster compounds wherein the phophinidene is a triply and less commonly doubly bridging ligand. One example is the ter-butylphosphinidene complex (t-BuP)Fe3(CO)10.[5] In clusters, phosphinidene is electronically similar to sulfide.

See also

References

  1. ↑ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "phosphanylidenes".
  2. ↑ Aktaş, H.; Slootweg, J.; Lammertsma, K. (2010). "Nucleophilic Phosphinidene Complexes: Access and Applicability". Angewandte Chemie International Edition in English. 49 (12): 2102–2113. doi:10.1002/anie.200905689. PMID 20157897.
  3. ↑ Marinetti, A.; Mathey, F.; Fischer, J.; Mitschler, A. (1982). "Generation and trapping of terminal phosphinidene complexes. Synthesis and x-ray crystal structure of stable phosphirene complexes". Journal of the American Chemical Society. 104 (16): 4484. doi:10.1021/ja00380a029.
  4. ↑ Hitchcock, P. B.; Lappert, M. F.; Leung, W. P. (1987). "The first stable transition metal (molybdenum or tungsten) complexes having a metal?phosphorus(III) double bond: the phosphorus analogues of metal aryl- and alkyl-imides; X-ray structure of [Mo(?-C5H5)2(?PAr)](Ar = C6H2But 3-2,4,6)". Journal of the Chemical Society, Chemical Communications (17): 1282. doi:10.1039/C39870001282.
  5. ↑ Gottfried Huttner, Konrad Knoll “RP-Bridged Metal Carbonyl Clusters: Synthesis, Properties, and Reactions” Angewandte Chemie International Edition in English 1987, Volume 26, 743-760. doi:10.1002/anie.198707431
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