Phosphinidene

From Wikipedia, the free encyclopedia
Jump to: navigation, search

Phosphinidenes (also: phosphanylidenes) in chemistry are chemical compounds containing a monovalent and diradical phosphorus atom. They are the phosphorus analogs of carbenes and nitrenes. The parent compound is phosphinidene (HP).[1] 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 isolable representatives of this group are [(OC)5W=P-Ph][2] and Cp2W=P-Mes*.[3] In this type of compound the M=P bond is a true double bond with strength increasing going down a row in the transition metal group.

In clusters[edit]

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.[4] In clusters, phosphinidene is electronically similar to sulfide.

See also[edit]

References[edit]

  1. ^ 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.  edit
  2. ^ 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.  edit
  3. ^ 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.  edit
  4. ^ 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