Retention of stereochemistry in the formation and fragmentation of diosmacyclobutanes, and other evidence against a diradical mechanism

Journal Article · Mon Aug 01 04:00:00 EDT 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00020a015· OSTI ID:6914727

Hembre, R T; Ramage, D L; Scott, C P; Norton, J R ^[1]

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1. Colorado State Univ., Fort Collins, CO (United States)

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.

• DOE Contract Number: FG03-94ER14405
• OSTI ID: 6914727
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:8; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKANES
ALKENES
CHEMICAL REACTIONS
CHEMISTRY
CYCLOALKANES
DEUTERIUM COMPOUNDS
ELEMENTS
ETHYLENE
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPOUNDS
PHOTOCHEMISTRY
RADICALS
REACTION INTERMEDIATES
REFRACTORY METAL COMPOUNDS
RESONANCE
STEREOCHEMISTRY
TRANSITION ELEMENT COMPOUNDS