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|Title:||Structural diversity in organotin compounds derived from bulky monoaryl phosphates: Dimeric, tetrameric, and polymeric tin phosphate complexes|
|Keywords:||Tetranuclear Organooxotin Cage|
|Publisher:||WILEY-V C H VERLAG GMBH|
|Citation:||EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (9), 1508-1517|
|Abstract:||Monoaryl phosphates with a bulky aryl substituent have been used to synthesize new organotin clusters and polymers. The equimolar reaction between 2,6-diisopropylphenylphosphate (dipp-H-2) and Me2SnCl2 in ethanol at 25 degrees C leads to the formation of [Me2Sn(mu(3)-dipp)](n) (1), while the reaction of 2,6-dimethylphenylphosphate (dmpp-H-2) with Me2SnCl2 in either a 1:1 or 2:1 molar ratio proceeds to produce exclusively [Me2Sn(mu-dmpp-H)(2)](n)center dot nH(2)O (2). Compounds 1 and 2 are 1D polymers with different architectures. In compound 1, the tin atom is five-coordinate (trigonal bipyramidal). Each dipp ligand bridges three different tin atoms to form an infinite ladder-chain structure. In 2, each six-coordinate (octahedral) tin atom is surrounded by four phosphate oxygen atoms originating from four different bridging dmpp-H ligands, thus forming a spirocyclic coordination polymeric chain. The use of nBu(2)SnO as the diorganotin source in its reaction with dipp-H-2 leads to the isolation of dimeric [nBu(2)Sn(mu-dipp-H)(dipp-H)](2) (4), which contains a central Sn2O4P2 unit. There are two chemically different half molecules of 4 in the asymmetric part of the unit cell and hence it actually exists as a 1:1 mixture of [nBu(2)Sn(mu-dipp-H)(dipp-H)](2) and [nBu(2)Sn(mu-dipp)(dipp-H-2)](2) in the solid state. The reaction of the monoorgano tin precursor nBuSn(O)(OH)center dot xH(2)O with dipp-H-2 takes place in acetone at room temperature to yield the tetrameric cluster 5, which has different structures in the solution and in the solid state. P-31 NMR spectroscopy clearly suggests that 5 has the formula [nBu(4)Sn(4)(mu-O)(2)(mu-dipp-H)(8)] in solution. The single-crystal Xray diffraction studies in the solid state, however, reveal that compound 5 exists as [nBu(4)Sn(4)(mu-OH)(2)(mu-dipp-H)(6)(mu-dipp)(2)]. The use of compounds 1-4 as possible precursors for the preparation of ceramic tin phosphate materials has been investigated. The thermolysis of 1 at 500 degrees C leads to the formation of quantitative amounts of Sn2P2O7, while the thermolysis of 2, 3, and 4 under similar conditions results in the formation of SnP2O7. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).|
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