Jump to main content
Jump to site search

Issue 37, 2012
Previous Article Next Article

Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(II) hydridocarbonyl and halocarbonyl pincer complexes

Author affiliations

Abstract

Reaction of the neutral PHNP ligand [HN(SiMe2CH2PPh2)2] with tungsten hexacarbonyl resulted in coordination of PHNP through both phosphorus donor atoms to form the tungsten complex [W(PHNP)(CO)4] (1). Reaction of PHNP with tris(acetonitrile)tricarbonyl tungsten gave both facial and meridional tridentate isomers [W(PHNP)(CO)3] (2-fac and 3-mer). These three d6 tungsten complexes could be interconverted under appropriate conditions. The thermodynamically favored isomer 3 was protonated to form seven-coordinate [W(PHNP)(CO)3H][BF4] (4). A related series of cationic tungsten(II) halide complexes was synthesized, [W(PHNP)(CO)3X]+ (6, X = I; 7, X = Br; 8, X = Cl; 9, X = F), by various routes. All of the tungsten(II) complexes underwent deprotonation at the amine site of the PHNP ligand when triethylamine was added, resulting in neutral seven-coordinate complexes. Variable temperature 1H, 31P{1H}, and 13C{1H} NMR spectroscopy showed fluxional behavior for all the seven-coordinate complexes reported here. Analysis of IR and NMR spectroscopic data showed trends through the series of coordinated halides. Crystal structures of tetracarbonyl 1, meridional tricarbonyl 3, and cationic hydride 4 were determined to confirm the coordination mode of the PHNP ligand.

Graphical abstract: Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(ii) hydridocarbonyl and halocarbonyl pincer complexes

Back to tab navigation

Supplementary files

Publication details

The article was received on 18 Apr 2012, accepted on 25 Jul 2012 and first published on 26 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT30848G
Citation: Dalton Trans., 2012,41, 11438-11448
  •   Request permissions

    Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(II) hydridocarbonyl and halocarbonyl pincer complexes

    L. A. Wingard, P. S. White and J. L. Templeton, Dalton Trans., 2012, 41, 11438
    DOI: 10.1039/C2DT30848G

Search articles by author

Spotlight

Advertisements