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Organotin(IV) compounds of the type (o-MeE-C6H4)CH2SnPh3-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3) and E = S, n = 0 (4), n = 1 (5), n = 2 (6). The complexes exhibit significant trigonal bipyramidal pentacoordination at tin as a consequence of intramolecular Sn-O (1-3) and Sn-S (4-6) interactions upon substitution of the phenyl groups by chloro groups. The intramolecular Sn-O distances in 1, 2, and 3 are 83%, 75%, and 79% of the sum of the van der Waals radii. The equivalent Sn-S values for 4, 5, and 6 are 90%, 73%, and 71%, respectively. The geometry of compound 3 is complicated by intermolecular dimerization via bridging chlorines creating a distorted octahedral geometry at tin. The related dichloro sulfur compound 6 also exhibits an intermolecular association in the form of Sn-Cl-H hydrogen bonding leading to a polymeric structure in the solid state. CPMAS 119Sn NMR spectroscopy suggests that the intramolecular Sn-E interactions persist in solution and also facilitated the discovery of a new crystalline form of 4, 4', that contains a Sn-S distance which is 95% the sum of the van der Waals radii.

The iridum-gallyl complex MeIr(PCy(3))(2)(GaMe(2))(Cl*GaMe(3)) exhibits a short Ir-Ga bond length of 2.381(1)-2.389(2) Å. Theoretical calculations (ZORA BP86/TZ2P) support the presence of a Ir-Ga single bond but highlight a π orbital contribution.

Racemic trinuclear diphenyltin(IV) cavitands and capsules have been assembled from diphenyltin(IV) and tris-dithiocarbamate ligands.

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