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Organoimido-complexes of Tungsten-(VI) -(V), and -(IV): Crystal and Molecular Structures of and .

DOI: 10.1039/DT9830002651

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2651 - 2656 (1983)

Update date:2022-08-05

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Authors:

Bradley, Donald C.Bradley, Donald C.

Hursthouse, Michael B.Hursthouse, Michael B.

Malik K. M. AbdulMalik K. M. Abdul

Nielson, Alastair J.Nielson, Alastair J.

Short Richard L.Short Richard L.

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Article abstract of DOI:10.1039/DT9830002651

Reaction of RNCO (R = Ph or Et) with WOCl4 gave the tungsten (VI) imido-compounds which, in further reactions gave (thf = tetrahydrofuran) and <3>.In the presence of phosphine ligands (L = PPh3 or PMe2Ph; L2 = Ph2PCH2CH2PPh2), in boiling benzene, reduction occured forming the paramagnetic tungsten (V) compounds 2>.More powerful reduction (sodium amalgam) in the presence of ligands (L = PMe3, PMe2Ph, and CNBut) gave the tungsten (IV) compounds 3>.Other reactions led to cleavage of the organoimido-group from the tungsten.An X-ray structure determination of showed the meridional configuration of chlorines with mutually trans-phosphines.The short W-N bond length (1.742 Angstroem) and practically linear WNC (172.3 degree) suggest that the imido-group is acting as a four electron ligand.Structure determination of shows that the three phosphines are meridional, and all cis to the W=-N-Ph unit.Although the imido-function seems to exert a small trans-lengthening influence on the relevant W-Cl bond in the trichloride, this effect does not seem to be present in the dichloride.

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