Structural features of di(1-adamantyl)benzylphosphane complexes of Cu(I) and Ag(I)

Add time:07/21/2019    Source:sciencedirect.com

The sterically bulky di(1-adamantyl)benzylphosphane (L) reacts with the copper(I) compounds, CuX (X = Cl, Br, I and SCN), in a 1:1 ratio to give the salts CuXL. Single crystal X-ray structures for X = Cl, Br and SCN, show that the complexes exist as dimeric species of the type [Cu2X2L2] with the X groups bridging to give each copper a distorted trigonal-planar coordination geometry with a ‘PX2’ donor site. When [Cu(CH3CN)4]BF4 reacts with L in a 1:2 ratio, the two-coordinated complex [CuL2]BF4 was formed which has a P–Cu–P angle of 169.46(6)°, reflecting the influence of the adamantyl groups. The silver(I) 1:2 compound, [AgClL2], has a ‘ClP2’ donor set with a distorted P–Ag–P bond angle of about 149.02(5)°. The reduced coordination numbers, irregular structures and distortions of selected angles are a result of the steric bulk (large cone angle) of L. Some of these structural features may also assist in understanding why Pd(0) complexes of L are effective catalysts for the Sonogashira coupling reactions of arylchlorides and alkynes.

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