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Coordination behavior and transformations of thienyl-substituted diacetylenes upon coordination to Os3H2(CO)10


Reference:

Brayshaw, S. K., Clarke, L. P., Homanen, P., Koentjoro, O. F., Warren, J. E. and Raithby, P. R., 2011. Coordination behavior and transformations of thienyl-substituted diacetylenes upon coordination to Os3H2(CO)10. Organometallics, 30 (15), pp. 3955-3965.

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    Official URL:

    http://dx.doi.org/10.1021/om200056c

    Abstract

    The reaction between 2- and 3-thienyl-substituted 1,3-butadiynes and the electron-deficient osmium cluster Os3H2(CO)10 yields trinuclear coordination products, associated with transformations of the diacetylene ligands. Depending on the heteroaryl end groups, osmium clusters with both a closed and open Os-triangle core were formed. The reaction between Os3H2(CO)10 and 1,4-bis(2-thienyl)butadiyne yielded [Os3(-H)(CO)10{(-n-(C 4H3S)(C8H4S)}] (1) and [Os 3(-H)(CO)10{(3-n2- n1-n1-(SC7H4)C(SC 4H3)}] (2), whereas in the analogous case of 1,4-bis(3-thienyl)butadiyne the main coordination product was found to be [Os3(-H)(CO)10{(-n-(C4H 3S)(C8H4S)}] (3). Compounds 1-3 were stable in air, but lost carbon monoxide upon prolonged heating. Thermal decarbonylation of 1 under N2 yielded a mixture of [Os3(-H)(CO) 9{(3-n3-(C4H 3S)(C8H4S)}] (4) and [Os3(-H) 2(CO)9{(3-n1- n1-(C4H3S)(C8H3S)}] (5). Thermal decarbonylation of 2 yielded [Os3(-H)(CO) 9{(3-n3-(C4H 3S)(C8H4S)}] (6), while thermal decarbonylation of 3 yielded [Os3(-H)(CO)9{(3- n3-(C4H3S)(C8H4S)}] (7). A reaction involving 3 with CF3COOH affords as the main cluster product the known cluster [Os3(-H)(CO)10(O 2CF3)] (8) and, unusually, permits the isolation and characterization of the novel organic molecule [(C4H 3S)(C8H4S)(OCF3)] (9) cleaved from the parent cluster. The structures of the new compounds were established by single-crystal X-ray studies and spectroscopic methods and supported by density functional theory.

    Details

    Item Type Articles
    CreatorsBrayshaw, S. K., Clarke, L. P., Homanen, P., Koentjoro, O. F., Warren, J. E. and Raithby, P. R.
    DOI10.1021/om200056c
    DepartmentsFaculty of Science > Chemistry
    Publisher StatementRaithby_Organometallics_30_15_3955.pdf: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/om200056c
    RefereedYes
    StatusPublished
    ID Code25482

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