MeSi(CH2SnRO)3 (R = Ph, Me3SiCH2): Building blocks for triangular-shaped diorganotin oxide macrocycles

The syntheses of the novel silicon-bridged tris(tetraorganotin) compounds MeSi(CH2SnPh2R)3 (2, R=Ph; 5, R=Me3SiCH2) and their halogen-substituted derivatives MeSi(CH2SnPh(3−n)In)3 (3, n=1; 4, n=2) and MeSi(CH2SnI2R)3 (6, R=Me3SiCH2) are reported. The reaction of compound 4 with di-t-butyltin oxide (t-Bu2SnO)3 gives the oktokaideka-nuclear (18-nuclear) molecular diorganotin oxide [MeSi(CH2SnPhO)3]6 (7) while the reaction of 6 with sodium hydroxide, NaOH, provides the trikonta-nuclear (30-nuclear) molecular diorganotin oxide [MeSi(CH2SnRO)3]10 (8, R=Me3SiCH2). Both 7 and 8 show belt-like ladder-type macrocyclic structures and are by far the biggest molecular diorganotin oxides reported to date. The compounds have been characterized by elemental analyses, electrospray mass spectrometry (ESI-MS), NMR spectroscopy, 1H DOSY NMR spectroscopy (7), IR spectroscopy (7, 8), and single-crystal X-ray diffraction analysis (2, 7, 8)

Tripod-shaped organotin compounds: complexation studies towards Lewis bases and chalcogenido clusters of unprecedented nuclearity

The principal axes of this thesis project are the synthesis of tripodal tris(organostannylmethyl)silanes of the type MeSi(CH2SnR(3–n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3) , as building blocks for the synthesis of novel organostannate complexes and umprecedented organotin chlacogeno-clusters among which novel triangular belt-shaped diorganotin oxo clusters [MeSi(CH2SnRO)3]n, R = Ph, CH2SiMe3 with gigantic nuclearity; oktokaideka (n = 18) and trikonta (n = 30). Furthermore, formation of new spacerbridgedtetrastannanesR'Sn(CH2SnR(3–n)Xn)3,(n=0–2;X=I,Cl;R=Ph,R'=R,X)andtheirattemptsfor complexation are reported. Moreover, there is synthesis of an unusual silicon-trimethylen-bridged double ladder organotin oxo cluster. Finally, new aminoalkanol-triorganostannane derivatives as precursors to build future tin-functionalized azidocryptands are reported. The numbering of compounds are only related in chapters 2 and 4, and independent in chapters 3 and 5- 6. The DVD contains Supporting Information of chapters 2- 6. In the second chapter, there is report of a series of novel silicon-bridged organotin compounds MeSi(CH2SnR(3–n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),2–12, their syntheses and characterization, in addition to the study of complexation behaviour of compounds4-7,9, and 12 with neutral and charged Lewis-base; Cl–, CH3COO–, F–, Br–, and HMPA. In the third chapter, synthesis and characterization of R'Sn(CH2SnR(3–n)Xn)3, (n = 0– 2; X = I, Cl; R = Ph, R'= R, X) derivatives are reported, and complexation attempts of derivative ClSn(CH2SnPhCl2)3, 3, with chloride anion give interesting binuclear and trinuclear organostannates6–9. In the fourth chapter, new ladder-type containing diorganotin oxo-clusters 26– 32, and first examples of organotinchalcogenidesS,Se-adamantane-typestructures,33–35,containingbothorganosiliconandorganotin moieties and their exchange reactions are reported. These chalcogeno organotin clusters are resulted from reactions of the halogenated precursors MeSi(CH2SnR(3–n)Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph, CH2SiMe3) with t-Bu2SnO, NaOH, EtOH, Na2S and Na2Se. In the fifth chapter, reaction of MeClSi((CH2)3SnMeCl2)2, 1, with pyridine gives the new double- ladder{[MeSi(MeSnCl)(CH2)3(µ3–O)(MeSnCl)(CH2)3]2O}2, 2 in which, layers are linked by eight siliconcontaining trimethylene chains and four silicon atoms are forming two siloxanes bridges. The final chapter reports synthesis and characterization of amino-stannane Ph3Sn(CH2)2NH2, 1, aminoalkanol organotin Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2 and spiro-type compound [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3 as potential precursors to synthesize future tin functionalized azido-cryptands