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Synthesis and X-ray structure of two isomeric aminocarbene complexes of tungsten containing a free carbon-carbon double bond
Institution:1. Department of Clinical Chemistry, University of Liège, CHU Sart-Tilman, Liège, Belgium;2. Laboratoire d''Exploitations fonctionnelles, Hôpital Necker-Enfants malades, Paris, France
Abstract:The reaction of allylamine with (CO)5WC(OCH2CH3)CH3 gives two isomeric aminocarbene complexes (CO)5WC(NHCH2CHCH2)CH3 2E and 2Z. Refluxing of a solution of this mixture in benzene gives the complexes (CO)4WC(η2NHCH2CHCH2)CH2 (3) and 2E, which have been separated. 2E was fully characterized by X-ray diffraction. Crystals of 2E are monoclinic, space group P21/n with Z = 4, a 7.188(3), b 14.312(2), c 12.530(2) Å and β 91.06(3)°.The same mixture when treated with lithium diisopropylamide (LDA) followed by allyl bromide gives a mixture of (CO)5WC(N(CH2CHCH2)2)CH3 (4) and 2Z. These complexes were separated, and 2Z fully characterized by X-ray diffraction. Crystals of 2Z are monoclinic, space group P21/c, with Z = 4, a 6.593(5), b 14.584(3), c 13.323(1) Å and β 95.13(4)°.
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