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Carbon−Fluorine Bond Cleavage in the Preparation of Osmium(III) and Osmium(IV) Fluorothiolate Complexes. Fluorine by Fluorine NMR-Assignment and Fluxional Processes

Supporting Info

Maribel Arroyo,*^† Sylvain Bernès,^‡ Margarita Cerón,^† Verónica Cortina,^† Consuelo Mendoza,^† and Hugo Torrens^§

Centro de Qumica del Instituto de Ciencias de la BUAP, Edificio 193 del Complejo de Ciencias, Ciudad Universitaria, San Manuel, 72570 Puebla, Puebla, Mexico, DEP, Facultad de Ciencias Qumicas, UANL, Guerrero y Progreso S/N, Col. Trevio 64570, Monterrey, N.L., Mexico, and Divisin de Estudios de Posgrado, Facultad de Qumica, UNAM, Ciudad Universitaria, 04510 Mxico D.F., Mexico

Inorg. Chem., 2007, 46 (12), pp 4857–4867

DOI: 10.1021/ic0619660

Publication Date (Web): May 16, 2007

To whom correspondence should be addressed. E-mail: slarroyo@siu.buap.mx.

†

Centro de Química del Instituto de Ciencias de la BUAP, Edificio 193 del Complejo de Ciencias, Ciudad Universitaria.

‡

Facultad de Ciencias Químicas, UANL.

División de Estudios de Posgrado, Facultad de Química, UNAM, Ciudad Universitaria.

Abstract

Reactions of OsO₄ with HSR (R = C₆F₅, C₆F₄H-4,) in refluxing ethanol afford (1) and (2), which involve the rupture of C−F bonds. At room temperature, the compound [Os(SC₆F₅)₃(PMe₂Ph)₂] or [Os(SC₆F₅)₄(PMe₂Ph)] reacts with KOH(aq) in acetone, giving rise to (3), through a process involving the rupture of two C−F bonds, while the compound [Os(SC₆F₄H)₄(PPh₃)] reacts with KOH(aq) in acetone to afford (4), which also implies a C−F bond cleavage. Single-crystal X-ray diffraction studies of 1, 2, and 4 indicate that these compounds include five-coordinated metal ions in essentially trigonal-bipyramidal geometries, whereas these studies on the paramagnetic compound 3 show a six-coordinated osmium center in a distorted octahedral geometry. ¹⁹F, ¹H, ³¹P{¹H}, and COSY ¹⁹F−¹⁹F NMR studies for the diamagnetic 1, 2, and 4 compounds, including variable-temperature ¹⁹F NMR experiments, showed that these molecules are fluxional. Some of the activation parameters for these dynamic processes have been determined.