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 and has only been observed in the gas phase and at cryogenic temperatures.

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 ed. 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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