Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Final report

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Assignment of the vibrational modes Of Os{sub 2}(CO){sub 8}(CHCH{sub 3}) and Os(CO){sub 4}(C{sub 2}H{sub 4)} has given fingerprint vibrational spectra for the following species when chemisorbed on metal catalyst surfaces: ethylidene and ethylene bound in a metallacyclopropane mode. The formation and fragmentation of diosmacyclobutanes have been shown to involve slippage of the outgoing olefin onto a single osmium, and associative exchange of the olefin from that site. The incorporation of vinylcyclopropane without rearrangement has confirmed the absence of a diradical intermediate. The anomalous stability of the diosmacyclobutane derived from trans-2-butene has proven due to greater destabilization (by the substituent methyls) … continued below

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17 p.

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Norton, J. R. April 25, 1994.

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Assignment of the vibrational modes Of Os{sub 2}(CO){sub 8}(CHCH{sub 3}) and Os(CO){sub 4}(C{sub 2}H{sub 4)} has given fingerprint vibrational spectra for the following species when chemisorbed on metal catalyst surfaces: ethylidene and ethylene bound in a metallacyclopropane mode. The formation and fragmentation of diosmacyclobutanes have been shown to involve slippage of the outgoing olefin onto a single osmium, and associative exchange of the olefin from that site. The incorporation of vinylcyclopropane without rearrangement has confirmed the absence of a diradical intermediate. The anomalous stability of the diosmacyclobutane derived from trans-2-butene has proven due to greater destabilization (by the substituent methyls) of the slipped intermediate than of the ground state. Reaction of an osmacyclobutane with 1,3- or 1,2-dienes (allenes) gives 1,2 rather than 1,4 addition to the diosmium unit. Treatment of Os(CO){sub 4}(C{sub 2}H{sub 4}) with triflic acid results in the formation of Os(CO){sub 4}(C{sub 2}H{sub 5})OTf. The authors have found that the reaction of an aryl iodine(III) reagent with propargyl stannanes or silanes results in o-iodo propargyl arenes.

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17 p.

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OSTI as DE94011211; Paper copy available at OSTI: phone, 865-576-8401, or email, reports@adonis.osti.gov

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  • Other Information: PBD: 25 Apr 1994

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  • April 25, 1994

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Norton, J. R. Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Final report, report, April 25, 1994; Fort Collins, Colorado. (https://digital.library.unt.edu/ark:/67531/metadc1311685/: accessed June 2, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.

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