Syntheses, Characterization, and Reactivity of Diruthenium Hydrido Complexes

• Published in: Organometallics 2016-04, Vol.35 (8), p.1079-1085
• Main Authors: Wiltse, Heather R, Johnson, Alyssa N, Durand, Raphael J, Brennessel, William, Chin, Robert M
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.6b00067

The reaction of [cis-{(η5-C5H3)2(CMe2)2}­Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2­(MeCN)2]­[OTf]2, 1, with H2 yields a μ-dihydrido complex, [cis-{(η5-C5H3)2(CMe2)2}­Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2­(μ-H)2]­[OTf]2, 2, in 79% yield. The reaction of 2 with Et3SiH affords a mono-μ-hydrido complex, cis-{(η5-C5H3)2(CMe2)2}­Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2­(μ-H)]­[OTf], 3. The reaction of either 2 or 3 (1–2 mol %) with C6H6 and Et3SiH results in the catalytic cleavage of the C–H bond in benzene along with the cleavage of the Si–Et bond to form PhEt2SiH (23–27% conversion) and C2H6. The reaction of 2 or 3 (1 mol %) with THF and Et3SiH results in the cleavage of the C–H bond in THF followed by the insertion of the SiEt2 group into the C–O bond, forming 2,2-diethyl-1-oxa-2-silacyclohexane (14% conversion) as one of the products.