Accession Number : ADA136991

Title :   Photochemical Conversion of H2Os3(CO)10(P-Donor) to H2Os3(CO)9(P-Donor) in Solution and on High Surface Area Silica.

Descriptive Note : Interim technical rept.,

Corporate Author : MASSACHUSETTS INST OF TECH CAMBRIDGE DEPT OF CHEMISTRY

Personal Author(s) : Bentsen,J G ; Wrighton,M S

PDF Url : ADA136991

Report Date : 28 Dec 1983

Pagination or Media Count : 18

Abstract : Near-UV irradiation of H2Os3(CO)10L yields conversion to the known coordinatively unsaturated H2Os3(CO)9L for L = PPh3 or PPh2Et in alkane solution at 298 K. Likewise, near-UV irradiation of an alkane suspension of (Si02)-L'Os3(CO)10H2 yields (Si02)-L'Os3(CO)9H2 where (Si02)-L'Os3(CO)10H2 is the solid prepared by reaction of high surface area Si02 with H2Os3(CO)10-(PPh2CH2CH2Si(OEt)3). The same photochemistry results at 77 K in rigid alkane glasses, but the initial (less than 5% conversion) product is not derived from loss of CO. Continued irradiation at 77 K yields H2Os3(CO)9L and CO, but H2Os3(CO)9L is only found in approx. 50% yield based on the amount of H2Os3(CO)10L consumed. Warming the irradiated sample to 298 K yields some regeneration of H2Os3(CO)10L and some additional H2Os3(CO)9L.

Descriptors :   *Photochemical reactions, *Ultraviolet radiation, *Irradiation, Hydrogen, Osmium, Carbon dioxide, Protons, Charge transfer, Alkanes, Solutions(General), Silicon dioxide, Chemical derivatives, Metals, Carbonyl compounds, Metal metal bonds, Cleavage, Clustering

Subject Categories : Radiation and Nuclear Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE