Photochemical Conversion of H2Os3(CO)10(P-Donor) to H2Os3(CO)9(P-Donor) in Solution and on High Surface Area Silica.
Interim technical rept.,
MASSACHUSETTS INST OF TECH CAMBRIDGE DEPT OF CHEMISTRY
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Near-UV irradiation of H2Os3CO10L yields conversion to the known coordinatively unsaturated H2Os3CO9L for L PPh3 or PPh2Et in alkane solution at 298 K. Likewise, near-UV irradiation of an alkane suspension of Si02-LOs3CO10H2 yields Si02-LOs3CO9H2 where Si02-LOs3CO10H2 is the solid prepared by reaction of high surface area Si02 with H2Os3CO10-PPh2CH2CH2SiOEt3. 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 H2Os3CO9L and CO, but H2Os3CO9L is only found in approx. 50 yield based on the amount of H2Os3CO10L consumed. Warming the irradiated sample to 298 K yields some regeneration of H2Os3CO10L and some additional H2Os3CO9L.
- Radiation and Nuclear Chemistry