Extremely bulky triarylphosphines incorporating 2,6-diisopropylphenyl substituents;: consideration of steric shielding and steric pressure

The geometry of 15 triarylphosphines which differ in the nature of the substituents at the 2 and 6 positions of one or more phenyl rings are compared. The sum of angles around phosphorus, Sigma{angle CPC}, is used as the primary measure of steric bulk. The roles of substituents, which act as steric shields surrounding the phosphine lone pair and of those which generate steric pressure and cause flattening of the C3P pyramid are identified. Both crystallographic and computational (HF 6-31G(d)) structures are used to assess Sigma{angle CPC}, the pyramidalization angle alpha, the average C-P distance, and the helical twist angle of the aryl rings beta. All of these parameters confirm that ortho-2,6-diisopropyl substituted aryl groups generate the most sterically congested triarylphosphines. Comparison to Tolman cone angles are made where these are available. (c) 2004 Elsevier B.V. All rights reserved.