- SYNTHESIS OF (M = Cr, Mo, or W; R = COPh or COC6H4Me-p) AND PHOTOCHEMICALLY INDUCED REACTIONS OF THE COMPLEX : CRYSTAL STRUCTURES OF THE COMPLEXES and
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Compounds of type (M = Cr, Mo, or W) are deprotonated by LiBun and the resultant carbanions are acylated by RCOCl (R = Ph or C6H4Me-p) to give the complexes .These acylated complexes react with NaOMe, reversibly, to give enolate anions or with RCOCl/pyridine to give the complex .Irradiation of gives, initially, the six-membered-ring chelate complex (3a), which is in turn converted into (4a) in the presence of light and traces of water.Crystals of both (3a) and (4a) are monoclinic, space group P21/c, with Z = 4.Those of (3a) have a = 17.013(3), b = 10.454(2), c = 19.723(3) Angstroem, and β = 114.23(1) deg.Those of (4a) have a = 18.629(3), b = 9.931(1), c = 18.182(4) Angstroem, and β = 94.58(1) deg.Final R factors were 0.030 for 3634 and 0.068 for 4027 observed reflections, respectively.
- Al-Jibori, Subhi,Hall, Michael,Hutton, Alan T.,Shaw, Bernard L.
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p. 863 - 868
(2007/10/02)
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- Alkylation and Acylation of Co-ordinated Tertiary Phosphines: the Nucleophilic Substitution of the Carbanions derived from 4(Ph2PCH2PPh2)> (M = Cr, Mo, or W)
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Complexes of the type are readily deprotonated by strong bases and the resultant carbanions attacked by nucleophiles such as MeI, EtI, CH2:CHCH2Cl, PhCH2Cl, Me3SiCl, Ph2PCl, PhCOCl, or MeC6H4COCl, to effect C-substitution.
- Al-Jibori, Subhi,Shaw, Bernard L.
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p. 286 - 287
(2007/10/02)
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