[Sn6(O)4(OSiMe3)4] and [{Sn(OSiMe3)2}2] have been used to deposit SnO thin films by chemical vapour deposition. Films derived from [Sn6(O)4(OSiMe3)4] comprise uniform cubes and are highly oriented, whereas those deposited from [{Sn(OSiMe3)2}2] are made up of a continuous non‐oriented layer with oriented cubes on the surface. The structure of a co‐crystal, 2 Sn6(O)4(OSiMe3)4⋅[Sn(OSiMe3)2]2⋅4 THF, shows that [{Sn(OSiMe3)2}2], a liquid at room temperature, adopts a μ‐OSiMe3‐bridged dimeric structure. [Sn6(O)4(OSiMe3)4] reacts with O2 in a controlled manner to afford the novel oxo‐cluster [Sn4(O)(OSiMe3)8], the structure of which is reported. In addition, a crystal of {[Sn4(O)(OSiMe3)5]+2[Sn(O)(OSiMe3)4Cl]+2}[Cl]−4 has been fortuitously isolated from the presence of SnCl2 in the starting material for the preparation of [Sn6(O)4(OSiMe3)4], and has been shown to incorporate two novel cationic oxo–tin clusters.
Reaction of [2‐{(CH2O)2CH}C6H4]Li with SnCl4 in a 4:1 molar ratio afforded [2‐{(CH2O)2CH}C6H4]4Sn (1), which was deprotected to give [2‐(O=CH)C6H4]4Sn (2). Homoleptic [2‐(RN=CH)C6H4]4Sn [R = Me2NCH2CH2 (3), 2,4,6‐Me3C6H2 (4), PhCH2 (5)] were obtained by condensation of 2 with the corresponding amine either in solution or by using a green, solvent‐free procedure for (imino)arylmetal species. All compounds were characterised by multinuclear NMR spectroscopy and mass spectrometry, and their molecular structures were determined by single‐crystal X‐ray diffraction. In all cases, the C4Sn core is distorted tetrahedral as a result of the combined effects of the intramolecular coordination of the heteroatoms from the organic ligands and the steric impediments imposed by the ligands. The overall coordination around tin was found to be different, that is, coordination numbers from six for 1 and 4, to seven for 3 and 5 and eight for 2. Compound 2 is the first example of a mononuclear tetraorganotin(IV) compound that contains an octacoordinated metal centre with a double helicate topology in the solid state. Multinuclear NMR spectroscopy studies in solutions of CDCl3 are consistent with equivalent organic groups attached to a tetracoordinate tin atom.
Organotin(iv) compounds might be used as linkers for building coordination polymers as suggested by the isolation of [{2-(OCH)C6H4}Me2SnO(O)CC5H4N-4]ZnTPP.
Hydrolysis of [2-{(CH2O)2CH}C6H4]2SnCl2 (1) [prepared from 2-[(CH2O)2CH]C6H4MgBr and SnCl4, in 2 : 1 molar ratio] gave [2-(O=CH)C6H4]2SnCl2 (2). Treatment of with the appropriate amine, in the absence of a solvent or catalyst, resulted in the isolation in high yields of [2-(RN[double bond, length as m-dash]CH)C6H4]2SnCl2 [R = 2'-C10H7 (3), 2',4',6'-Me3C6H2 (4), PhCH2 (5), Me2NCH2CH2 (6), 2'-PyCH2 (7)]. The reaction of with [Pd(COD)Cl2] provided the heterometallic species [Cl2Pd{2-(2'-PyCH2N[double bond, length as m-dash]CH)C6H4}2SnCl2] (8). The compounds were characterised by multinuclear NMR spectroscopy in solution, and mass spectrometry and IR spectroscopy in the solid state. The molecular structures of 1, 2, 4-7 and 8·CH3CN were established by single-crystal X-ray diffraction. For all diorganotin(IV) dichlorides intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted octahedral (C,E)2SnCl2 core (E = O, N). The presence of intramolecular N→Sn interactions in solution, responsible for the restriction of free rotation of mesityl groups around the C-N(=C) single bonds, is suggested by (1)H and (13)C NMR data. In the heterometallic dinuclear complex 8 the octahedral coordination around tin is preserved as in 7 and the nitrogen atoms from the pyridyl groups in the pendant arms are coordinated to palladium, leading to a trans-square planar PdCl2N2 core.
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