Stable Versions of Transient Push-Pull Carbenes: Extending Lifetimes from Nanoseconds to Weeks

• Published in: Science (American Association for the Advancement of Science) Vol. 288; no. 5467; pp. 834 - 836
• Main Authors: Buron, Christophe, Gornitzka, Heinz, Romanenko, Vadim, Bertrand, Guy
• Format: Journal Article
• Language: English
• Published: Washington, DC American Society for the Advancement of Science 05.05.2000; American Association for the Advancement of Science
• Subjects: Alkenes; Astronomical objects; Carbenes; Carbon compounds; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Orbitals; Organic compounds; Organometalloidal and organometallic compounds; Phosphorus; Photolysis; Physics; Pixels; Radar; Radar tracking; Solvents; Structure of liquids; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Time-dependent properties; relaxation; United States; Substituent effect; Chemical solution; Lifetime; Molecular structure; Stabilization; Push pull compound; XRD; Experimental study; Carbenes; Phosphorus Organic compounds; Crystal structure
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.288.5467.834

A (phosphanyl)(trifluoromethyl)carbene is shown to be stable for weeks in solution at temperatures up to -30°C;. Its chemical behavior exactly matches that of its transient congeners, even to the extent that subtle effects, such as the recently discovered weak π interaction with aromatics, are observed. The influence of substituents on the structure of push-pull carbenes is demonstrated by a single-crystal x-ray diffraction study of a (phosphanyl)[2,6-bis(trifluoromethyl)phenyl]carbene. The lifetime of these molecules makes them accessible to a wider range of standard techniques, allowing their chemical and physical behaviors to be studied in more detail than was previously possible.