P. R. Markies, R. Altink, A. Villena
Jan 8, 1991
Citations
0
Influential Citations
21
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract A series of phenylmagnesium bromides (1, 3–8) with ortho-substutients capable of forming intra-molecular coordinative bonds along with the correspondng diarylmagnesium compounds (1a, 3a–6a, 8a) have been synthesized. The thermodynamic parameters ΔHs, and ΔSs for the Schlenk equilibria (2 ArMgBr &/rhar2; Ar2Mg + MgBr2) have been determined by variable temperature NMR spectroscopy. Crystal structures were obtained of 5,6,7,8,9-tetrahydrodibenz[d,g][1,6]oxamagnesecin (2a) and bis(2,6-di(methoxymethyl)phenyl)magnesium (4a). The extent of intramolecular coordination in these compounds as determined in the solid state, is used in the discussion of the influence of substituents on the Schlenk equilibrium parameters. Unusual penta- or hexa-coordination is encountered and explained as a consequence of intramolecular coordination.