Circumambulatory rearrangement with characteristics of a 2:1 covalent molecular bevel gear

J Am Chem Soc. 2006 Sep 20;128(37):12169-73. doi: 10.1021/ja0627895.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bridged Bicyclo Compounds / chemistry*
  • Cycloparaffins / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Organophosphorus Compounds / chemistry*
  • Thermodynamics
  • Tungsten Compounds / chemistry*

Substances

  • Bridged Bicyclo Compounds
  • Cycloparaffins
  • Organophosphorus Compounds
  • Tungsten Compounds