Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 12, 1990
Previous Article Next Article

Electron paramagnetic resonance study of the [W(CO)4{P(OMe)3}] radical anion trapped in a single crystal of [N(PPh3)2][W(CO)4H{P(OMe)3}]

Abstract

Gamma-irradiated single crystals of [N(PPh3)2][W(CO)4H{P(OMe)3}] contain an anisotropic e.p.r. signal which exhibits hyperfine coupling to a single 31P nucleus. X-Ray crystallography showed that the crystals belonged to the orthorhombic system (Pbca), with a= 15.562 6(21), b= 19.980(3), c= 27.161(4)Å, and Z= 8; the undamaged anion had an approximately octahedral geometry in which the H atom was cis to the phosphite ligand. Crystallographically aligned specimens were used to determine both the g and the 31P hyperfine interaction tensors [g= 2.0708, 2.0740, 1.9914; a(31P)= 75.1, 68.4, 45.5 MHz] and their direction cosines in the crystal-axis system. The form of the g tensor and the alignment of gmin. with the H–W–Cax. direction of the undamaged anion point to considerable unpaired spin density in the W 5dz2 orbital. Alignment of the 31P tensor along gmin. and the W–P bond is attributed to direct overlap of the P 3pz orbital with the metal atomic orbital. Comparison with other 31P hyperfine measurements suggests that e.p.r. provides a good indication of the efficiency of back-bonding in such organometallic radicals.

Back to tab navigation

Article type: Paper
DOI: 10.1039/DT9900003655
Citation: J. Chem. Soc., Dalton Trans., 1990,0, 3655-3661

  •   Request permissions

    Electron paramagnetic resonance study of the [W(CO)4{P(OMe)3}] radical anion trapped in a single crystal of [N(PPh3)2][W(CO)4H{P(OMe)3}]

    R. C. Hynes, K. F. Preston, J. J. Springs and A. J. Williams, J. Chem. Soc., Dalton Trans., 1990, 0, 3655
    DOI: 10.1039/DT9900003655

Search articles by author

Spotlight

Advertisements