Circumambulatory rearrangement with characteristics of a 2:1 covalent molecular bevel gear.
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.
Bulo
Rosa E
RE
Department of Chemistry and Applied Biosciences, ETH Zürich, USI-Campus, Via Giuseppe Buffi 13, 6900 Lugano, Switzerland.
Allaart
Florian
F
Ehlers
Andreas W
AW
de Kanter
Franciscus J J
FJ
Schakel
Marius
M
Lutz
Martin
M
Spek
Anthony L
AL
Lammertsma
Koop
K
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*
D001643:Bridged Bicyclo Compounds; D003516:Cycloparaffins; D009943:Organophosphorus Compounds; D017973:Tungsten Compounds