Synthesis and reactivity of molybdenum complexes containing functionalized alkynyl ligands: A photochemically activated CO-releasing molecule (PhotoCO-RM)

David Zhang, A.J. Atkin, I.J.S. Fairlamb, A.C. Whitwood, J.M. Lynam

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Reaction of [MoCl(η-CH)(CO) ] with propargyl alcohols HC≡CCRROH in the presence of catalytic amounts of CuI and using NEtH as solvent results in the formation of alkynyl complexes [Mo(C≡CCRR OH)(η-CH)(CO)]. The structure of the complexes where R = R = Me and R = Me, R = Ph were confirmed by single-crystal X-ray diffraction. The method could be extended to a range of propargyl ethers and propargyl esters, which allowed for the preparation of molybdenum complexes containing pendant salicylate and β-d-fructopyranose groups. The alkynyl complex [Mo(C≡CCHOH)(η-CH )(CO)] undergoes a further reaction with NEt H to give the substituted allyl complex [Mo(η-H CC{NEt}CHC{O}NEt)(η-C H)(CO)]. Similar products could be obtained from the reaction of [MoCl(η-CH)(CO) ] with HC≡CCHOH in the presence of CuI using pyrrolidine or piperidine as solvent. In the case of the reaction with piperidine a further product could be isolated that has arisen from the coupling of two propargyl alcohol molecules to afford a butadienyl ligand. The CO-releasing properties of a number of these novel complexes have been investigated. In the case of the water-soluble alkynyl complex containing a β-d-fructopyranose group CO release was shown to be promoted by exposure to UV light, revealing a new class of photochemically activated CO-releasing molecules (PhotoCO-RMs).
Original languageEnglish
Pages (from-to)4643-4654
Number of pages12
Issue number17
Publication statusPublished - 12 Sept 2011

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