{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T01:00:10Z","timestamp":1759971610362,"version":"build-2065373602"},"reference-count":97,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2011,8,18]],"date-time":"2011-08-18T00:00:00Z","timestamp":1313625600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2011,11,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Two cyclopropyl allenylidene complexes [Ru]=C\uf8feC\uf8feC(R)(C<jats:sub>3<\/jats:sub>H<jats:sub>5<\/jats:sub>) ([Ru]=[RuCp(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>], Cp=Cyclopentadienyl; R=thiophene (<jats:bold>2a<\/jats:bold>) and R=Ph (<jats:bold>2b<\/jats:bold>)) are prepared from the reactions of [Ru]Cl with the corresponding 1\u2010cyclopropyl\u20102\u2010propyn\u20101\u2010ol in the presence of KPF<jats:sub>6<\/jats:sub>. Thermal treatment, halide\u2010anion addition, and palladium\u2010catalyzed reactions of <jats:bold>2a<\/jats:bold> and <jats:bold>2b<\/jats:bold> all lead to a ring expansion of the cyclopropyl group, giving the vinylidene complexes <jats:bold>4a<\/jats:bold> and <jats:bold>4b<\/jats:bold>, respectively, each with a five\u2010membered ring. This ring expansion proceeds by C\uf8ffC bond formation between C\u03b2 of the cumulative double bond and a methylene group of the cyclopropyl ring. In the reaction of <jats:bold>2a<\/jats:bold> with pyrrole, consecutive formation of two C\uf8ffC bonds, one between C\u20102 of pyrrole and C\u03b3 of <jats:bold>2a<\/jats:bold> and the other between C\u20103 of pyrrole and C\u03b1, results in the formation of <jats:bold>6a<\/jats:bold>. The reaction proceeds by addition of pyrrole and 1,3\u2010proton shifts. The hydrogenation of <jats:bold>2a<\/jats:bold> by NaBH<jats:sub>4<\/jats:sub> is carried out in different solvents. The cumulative double bonds are reduced regioselectively to give a mixture of <jats:bold>7a<\/jats:bold> and <jats:bold>8a<\/jats:bold>. Interestingly, use of different solvents leads to different ratios of <jats:bold>7a<\/jats:bold> and <jats:bold>8a<\/jats:bold>. Presence of a protic solvent like methanol in dichloromethane or chloroform solution increases the yield of <jats:bold>8a<\/jats:bold>, thus revealing that both the rates of hydroboration and deboronation increase. The structures of two new complexes <jats:bold>4a<\/jats:bold> and <jats:bold>6a<\/jats:bold> have been firmly established by X\u2010ray diffraction analysis.<\/jats:p>","DOI":"10.1002\/asia.201100297","type":"journal-article","created":{"date-parts":[[2011,8,18]],"date-time":"2011-08-18T11:16:48Z","timestamp":1313666208000},"page":"3122-3131","source":"Crossref","is-referenced-by-count":6,"title":["Reactions of Ruthenium\u2013Allenylidene Complexes Tethering a Cyclopropyl 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