Hypervalent organotin(IV) derivatives containing [2-(Me2NCH2)C6H4]Sn moieties. Competition between nitrogen and chalcogen atoms for coordination to the metal centre

[2-(Me2NCH2)C6H4]SnPh2Cl (1) was prepared by reacting Ph2SnCl2 with [2-(Me2NCH2)C6H4]Li in toluene. The reactions of (1) with the ammonium salt of the appropriate thiophosphinato ligand in 1:1 molar ratio afford the isolation of [2-(Me2NCH2)C6H4]SnPh2L [L=S(S)PPh2 (2), O(S)PPh2 (3)] as white crystalline solids. The molecular structure of 1–3 was determined by single-crystal X-ray diffraction. Their crystals contain monomeric units with the metal atom exhibiting a distorted trigonal bipyramidal coordination environment. The SnC3 moiety is almost planar. The N atom of the pending CH2NMe2 arm is strongly coordinated to the metal centre (Sn(1)N(1) 2.519(2), 2.548(3), 2.481(2) Å for 1, 2 and 3, respectively), trans to the Cl, O or S atoms (N(1)Sn(1)Cl(1) 170.49(6)°, N(1)Sn(1)S(1) 169.06(8)°, N(1)Sn(1)O(1) 168.58(8)°, respectively). The S atom double bonded to phosphorus is not involved in intra- or intermolecular coordination to tin.