Gerald Doyle

Carbonyl (η3-allyl) anions of molybdenum and tungsten

Abstract Anionic complexes of the type [M(CO)2(diket)(η3-allyl)Cl]− (where M is Mo or W and diket is a β-diketonate group) are readily prepared by the addition of allyl chloride to [M(CO)4(diket)]− anions. NMR measurements indicate an equilibrium between two conformers due to rotation of the allyl groups. [M(CO)5(OC(=O)R)]− anions also react with allyl chloride to form η3-allyl complex anions. Some structural aspects of both the diketonate and carboxylate derivatives are discussed.

Pentacarbonylcarboxylate anions of the group VI transition metals

Abstract Pentacarbonylcarboxylate anions of Cr, Mo and W were prepared either directly from the metal hexacarbonyls or by reaction of a thallium(I) carboxylate with the pentacarbonyl halide ions. The infrared spectra indicate that the complexes deviate significantly from C 4 v symmetry. Cotton—Kraihanzel force constants for a number of complexes were calculated and compared.

Anionic carbonyl complexes of the group VI transition metals with sulfur containing ligands

Anionic complexes of the type [M(CO)4(dpet)]− (where M is Cr, Mo or W and dpet is the anion of 2-(diphenylphosphino)ethanthiol) are readily prepared by the reaction of the Tl(dpet) and [M(CO)5X]− anions (X = halogen). These complex anions appear to have the normal octahedral geometry with the dpet ligand coordinated through both the P and S atoms. When treated with methyl or allyl halides, neutral complexes of the type M(CO)4(dpet—R) are formed (where R is an allyl or methyl group now bound to the sulfur atom). By treating TlI salts of o-aminothiophenol (atp), o-methylmercaptophenol (nmp) and methylxanthic acid (mxt), with [M(CO)5]− anions, the respective complexes [M(CO)4(atp)]−, [M(CO)4(mmp)]− and [M(CO)5(mxt)]− are formed.

The reaction of formyl fluoride with transition metal complexes

Abstract Formyl fluoride reacts with metal carbonyl anions in a manner similar to acetic formic anhydride. Although formyl complexes may have been formed as unstable intermediates, no neutral formyl complexes could be isolated but rather the expected decomposition products, the metal carbonyl hydrides or ?imers, were produced. The attempted oxidative addition of formyl fluoride to various coordinately unsaturated metal complexes also did not result in the formation of formyl derivatives. HF adducts were obtained from the reaction ?fIr(CO)Cl(PR 3 ) 2 or M(PPh 3 ) 4 (M Pt or Pd) with formyl fluoride whereas Ru(NO)Cl(PPh 3 ) 2 and Rh(PPh 3 ) 3 Cl give the CO complexes Ru(NO)(CO)Cl(PPh 3 ) 2 and Rh(CO)Cl(PPh 3 ) 2 , respectively.

The preparation and crystal structure of (η-C5H5)Ru[(C6H5)3P]2(CO)5Co·THF

Abstract The reaction of (η-C5H5)Ru[(C6H5)3P]2Cl with Co(CO)4− leads to a mixture of metal containing products. One of these products (η5-C5H5)Ru[(C6H5)3P]2(CO)5Co·THF was isolated in pure form and its structure determined. The complex crystallizes in space group P21/n with a 15.015(1), b 18.543(3), c 16.984(2) A, β 110.75(1)°, V = 4422 A3 and Z = 4. The structure has been refined to R = 0.072, Rw 0.073 for 3643 observed reflections. The molecule consists of a (η5-C5H5)Ru[(C6H5)3P]2(CO)+ cation a Co(CO)4− anion and a THF molecule of crystallization. The cation has a typical “piano-stool” structure and the Co(CO)4− anion has a nearly ideal tetrahedral configuration.

Dicarbonyl allyl derivatives of molybdenum and tungsten containing β-diketonate substituents

Abstract A number of complexes of the type M(CO)2(η3-allyl)(diket)L (where M is Mo or W, diket is a β-diketonate group and L is pyridine, tetrahydofuran or acetonitrile) have been prepared and characterized by elemental analysis and IR and NMR spectroscopy. These complexes apparently adopt an octahedral configuration similar to related neutral species but spectroscopic data indicate an equilibrium between two conformers probably due to rotation of the allyl groups.