Asymmetric pentameric and tetrameric organooxotin clusters: Insights into their formation through partial dearylation

Abstract

The reaction between diphenyltin dichloride and 2,6-diisopropylphenylphosphate (dippH(2)) in ethanol affords a highly asymmetric pentameric organotin cluster, [Sn5Ph7(mu(3)-dipp)(4)(mu-dippH)(mu(3)-O)(mu-OEt)(EtOH)(H2O)Cl] center dot H2O (1), that contains Ph-, EtO-, Cl-, O-2(-), ROPO32-, ROPO3H-, OH2, and EtOH ligands. The same reaction when carried out in iPrOH, under otherwise identical conditions, results in the formation of another pentamer, [Sn5Ph7(mu(3)-dipp)(4)(mu-dippH)(mu(3)-O)(mu-OH)(iPrOH)(H2O)Cl] center dot iPrOH (2). Change of the phosphate ligand to sterically less bulky 2,6-dimethylphenylphosphate in the above reaction carried out in ethanol results in the formation of a tetrameric cluster, [Sn4Ph5(mu(3)-dmpp)(2)(mu-dmpp)(mu-dmppH)(2)(mu(3)-O)(mu-OEt)(EtOH)] center dot EtOH (3). Isolation of 3 provides useful insights into the formation of the pentamers 1 and 2. Compounds 1-3 have been characterized by means of their analytical data, IR, and multinuclear NMR (H-1, P-31, and Sn-119) spectral data. The solid-state structures of 1-3 have been determined by X-ray diffraction studies.