Retention of Stereochemistry in the Formation and Fragmentation of Diosmacyclobutanes, and Other Evidence against a Diradical Mechanism
Two results argue against a diradical intermediate in the exchange of diosmacyclobutanes with free olefins. The diosmacyclobutane Os[sub 2](CO)[sub 8]([mu]-propene) reacts with vinylcyclopropane to give as the sole product a diosmacyclobutane bearing an intact cyclopropane ring. Repeated exchange of...
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| Veröffentlicht in: | Organometallics 1994-08, Vol.13 (8), p.2995-3001 |
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| creator | Hembre, Robert T Ramage, David L Scott, Carl P Norton, Jack R |
| description | Two results argue against a diradical intermediate in the exchange of diosmacyclobutanes with free olefins. The diosmacyclobutane Os[sub 2](CO)[sub 8]([mu]-propene) reacts with vinylcyclopropane to give as the sole product a diosmacyclobutane bearing an intact cyclopropane ring. Repeated exchange of trans-ethylene-1,2-d[sub 2] with the same ligand in a diosmacyclobutane shows >99.1% stereochemical excess per exchange half-life. These exchange reactions do not involve mononuclear olefin complexes. 36 refs. |
| doi_str_mv | 10.1021/om00020a015 |
| format | Article |
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The diosmacyclobutane Os[sub 2](CO)[sub 8]([mu]-propene) reacts with vinylcyclopropane to give as the sole product a diosmacyclobutane bearing an intact cyclopropane ring. Repeated exchange of trans-ethylene-1,2-d[sub 2] with the same ligand in a diosmacyclobutane shows >99.1% stereochemical excess per exchange half-life. 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The diosmacyclobutane Os[sub 2](CO)[sub 8]([mu]-propene) reacts with vinylcyclopropane to give as the sole product a diosmacyclobutane bearing an intact cyclopropane ring. Repeated exchange of trans-ethylene-1,2-d[sub 2] with the same ligand in a diosmacyclobutane shows >99.1% stereochemical excess per exchange half-life. These exchange reactions do not involve mononuclear olefin complexes. 36 refs.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/om00020a015</doi><tpages>7</tpages></addata></record> |
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| source | ACS Publications |
| subjects | 400102 -- Chemical & Spectral Procedures 400500 -- Photochemistry ALKANES ALKENES CHEMICAL REACTIONS CHEMISTRY CYCLOALKANES DEUTERIUM COMPOUNDS ELEMENTS ETHYLENE Exact sciences and technology HYDROCARBONS HYDROGEN HYDROGEN COMPOUNDS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY MAGNETIC RESONANCE NONMETALS NUCLEAR MAGNETIC RESONANCE Organic chemistry ORGANIC COMPOUNDS ORGANOMETALLIC COMPOUNDS Organometalloidal and organometallic compounds OSMIUM COMPOUNDS PHOTOCHEMISTRY Preparations and properties RADICALS REACTION INTERMEDIATES REFRACTORY METAL COMPOUNDS RESONANCE STEREOCHEMISTRY TRANSITION ELEMENT COMPOUNDS 400201 -- Chemical & Physicochemical Properties Transition metals derivatives |
| title | Retention of Stereochemistry in the Formation and Fragmentation of Diosmacyclobutanes, and Other Evidence against a Diradical Mechanism |
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