title: Circumambulatory rearrangement with characteristics of a 2:1 covalent molecular bevel gear.
abstract: anti-W(CO)(5)-complexed 9-methyl-9-phosphabicyclo[6.1.0]nonatriene represents a covalently interlocked molecular bevel gear. Correlated movement of the phosphorus atom and the eight-membered ring by way of a "walk" rearrangement makes gear slippage impossible. The gearing motion is transferred to the four-toothed W(CO)(5) propeller connected to the rotating phosphorus atom, enabling a gearing ratio of 2:1 according to B3LYP and Car-Parrinello Molecular Dynamics calculations. Methyl substitution of the eight-membered ring tempers the gearing process, with the PMeW(CO)(5) entity passing the substituted carbon atom only at temperatures above 50 degrees C.
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, USI-Campus, Via Giuseppe Buffi 13, 6900 Lugano, Switzerland.
authors.forename: Rosa E
authors.initials: RE
authors.lastname: Bulo
authors.forename: Florian
authors.initials: F
authors.lastname: Allaart
authors.forename: Andreas W
authors.initials: AW
authors.lastname: Ehlers
authors.forename: Franciscus J J
authors.initials: FJ
authors.lastname: de Kanter
authors.forename: Marius
authors.initials: M
authors.lastname: Schakel
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.forename: Anthony L
authors.initials: AL
authors.lastname: Spek
authors.forename: Koop
authors.initials: K
authors.lastname: Lammertsma
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D003516:Cycloparaffins / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009943:Organophosphorus Compounds / Q000737:chemistry*; D013816:Thermodynamics; D017973:Tungsten Compounds / Q000737:chemistry*
chemical_list: D001643:Bridged Bicyclo Compounds; D003516:Cycloparaffins; D009943:Organophosphorus Compounds; D017973:Tungsten Compounds