Synthesis of [M(CO)4(Ph2PCHRPPh2)](M = Cr, Mo, or W; R = COPh or COC6H4Me-p) and photochemically induced reactions of the complex [W(CO)4{Ph2PCH(COPh)PPh2}]: crystal structures of the complexes [W(CO)4{Ph2POC(Ph)CHPPh2}] and [W(CO)4(PPh2OH)(PPh2CH2COPh)] Academic Article uri icon

abstract

  • full title: Synthesis of [M(CO)4(Ph2PCHRPPh2)] (M = Cr, Mo, or W; R = COPh or COC6H4Me-p) and photochemically induced reactions of the complex [W(CO)4{Ph2PCH(COPh)PPh2}]: crystal structures of the complexes [W(CO)4{Ph2POC(Ph)=CHPPh2}] and [W(CO)4(PPh2OH)(PPh2CH2COPh)] Compounds of type [[graphic omitted]Ph2)] (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 [[graphic omitted]Ph2}]. These acylated complexes react with NaOMe, reversibly, to give enolate anions [[graphic omitted]Ph2}] or with RCOCl/pyridine to give the complex [[graphic omitted])2C=CR(OCOR)}]. Irradiation of [[graphic omitted]Ph2}] gives, initially, the six-membered-ring chelate complex [[graphic omitted]Ph2}] (3a), which is in turn converted into [W(CO)4(PPh2OH)(PPh2CH2COPh)] (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) , and = 114.23(1). Those of (4a) have a = 18.629(3), b = 9.931 (1), c = 18.182(4) , and = 94.58(1). Final R factors were 0.030 for 3 634 and 0.068 for 4 027 observed reflections, respectively.

published proceedings

  • J. Chem. Soc., Dalton Trans.

author list (cited authors)

  • Al-Jibori, S., Hall, M., Hutton, A. T., & Shaw, B. L.

citation count

  • 29

complete list of authors

  • Al-Jibori, Subhi||Hall, Michael||Hutton, Alan T||Shaw, Bernard L

publication date

  • January 1984