Phosphinidene

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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.

Monomeric phosphinidinesEdit

Using very bulky substituents, a phosphinidine has been isolated at room temperature. With the formula R2P-P, the compound reacts with isocyanides and alkenes to give stable adducts.[3]

Phosphinidine complexesEdit

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][4] and Cp2W=P-Mes*.[5]

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.[6]

See alsoEdit

ReferencesEdit

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "phosphanylidenes". doi:10.1351/goldbook.P04549
  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. ^ Liu, Liu; Ruiz, David A.; Munz, Dominik; Bertrand, Guy (2016). "A Singlet Phosphinidene Stable at Room Temperature". Chem. 1: 147-153. doi:10.1016/j.chempr.2016.04.001.
  4. ^ 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.
  5. ^ 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.
  6. ^ Huttner, Gottfried; Knoll, Konrad (1987). "RP-Bridged Metal Carbonyl Clusters: Synthesis, Properties, and Reactions". Angewandte Chemie International Edition in English. 26 (8): 743–760. doi:10.1002/anie.198707431.