Hydrolysis products of diorganotin dihalides. I. Bis[1,3-dihydroxo-1,1,3,3-tetrakis(2-methyl-2-phenylpropyl)distannoxane]

Abstract

In the solid state, the title compound, di‐μ‐hydroxo‐1:2κ2O;‐3:4κ2O‐dihydroxo‐1κO,4κO‐octakis(2‐methyl‐2‐phenyl­propyl)‐1κ2C,2κ2C,3κ2C,4κ2C‐di‐μ3‐oxo‐1:2:3κ3O;2:3:4κ3O‐tetratin(IV), [Sn4O2(OH)4(C10H13)8], forms centrosymmetric dimeric [(Neophyl2SnOH)(Neophyl2SnOH)O]2 mol­ecules (Neophyl = 2‐methyl‐2‐phenylpropyl), with an almost planar Sn–O framework that adopts a ladder‐type structure consisting of three four‐membered rings. The hydroxyl groups are shielded by the organic groups, which prevent them from further condensation and from the formation of hydrogen bonds.

Hydrolysis of Bis((trimethylsilyl)methyl)tin Dihalides. Crystallographic and Spectroscopic Study of the Hydrolysis Pathway

“…This effect is even more pronounced for the related unsymmetrically substituted tetraorganodistannoxane [t-Bu 2 (Cl)SnOSn(Cl)CH 2 SiMe 3 ] 2 (C-Sn-C ) 146.7(2)°, Sn‚‚‚Cl ) 3.115(2) Å). 29 In contrast to compound 6, with an intramolecular Sn‚‚‚OH distance of 3.583(5) Å being close to the sum of the van der Waals radii 52b of tin and oxygen (1.50 Å) and being associated with a C-Sn-C angle of 119.7(3)°(see above), the shortening of this distance to 3.429 (11) Å in the related derivative [t-Bu 2 (OH)SnOSn(OH)CH 2 SiMe 3 ] 2 29 is suf- The Sn(endo)-X-Sn(exo) bridges are unsymmetric, with distances of 2.5775(15)/2.9206 and 2.5865(16)/ 2.8574(16) Å for 3 (X ) Cl(1), Cl(2)), 2.147(4)/2.342(4) Å for 6 (X ) O(1)), and 2.26(2)/2.32(2) and 2.24(2)/2.40-(2) Å for 8 23 (X ) O(3), O(4)). The asymmetry of the axial Sn-X and Sn-Y bonds amounts to 0.5266 and 0.4437 Å for 3 (X ) Cl(1), Y ) Cl(3) and X ) Cl(2), Y ) Cl(4)), 0.3100 Å for 6 (X ) O(1), Y ) O(3)), and 0.20 and 0.09 Å for 8 23 4)), while the asymmetry of the axial Sn-X and Sn-O bonds amounts to 0.3745 and 0.3955 Å for 3 (X ) Cl(1), Cl(2)), 0.018 Å for 6 (X ) O(1)), and 0.09 and 0.08 Å for 8 23…”

“…(Me3SiCH2)2SnPh2 was synthesized according to a literature procedure. 43 Solution 1 H, 13 C, 19 F, 29 Si, and 119 Sn NMR spectra were recorded on a Bruker DRX 400 or DPX 300 instrument at 400.13 ( 1 H), 100.31 ( 13 C), 282.40 ( 19 F), 79.49 ( 29 Si), and 149.20 MHz ( 119 Sn) in CDCl3 (unless otherwise stated) and were referenced to SiMe4 ( 1 H, 13 C, 29 Si), CFCl3 ( 19 F), or SnMe4 ( 119 Sn). 119 Sn MAS NMR spectra were obtained from a Bruker MSL 400 spectrometer using cross-polarization and high-power proton decoupling.…”

“…16 A large number of these compounds has been investigated by X-ray diffraction studies. [21][22][23][24][25][26][27][28][29][30][31] ing only two different types of donors, e.g. X, Y ) Cl, OH, two symmetrically substituted dimeric tetraorganodistannoxanes, [R 2 (X)SnOSn(Y)R 2 ] 2 (X ) Y ) Cl; X ) Y ) OH), and an unsymmetrically substituted dimeric tetraorganodistannoxane, (X ) Cl, Y ) OH), are preferably realized.…”

First Example of a Hydrogen-Bonded Three-Dimensional Pillared Structure Involving an Organotin Motif: Synthesis and X-ray Crystal Structures of {[nBu2Sn(H2O)3(L)Sn(H2O)3nBu2]2+[L]2-}·2MeOH·2H2O and {[Ph3Sn(L)Sn(H2O)Ph3]n}·THF (L = 1,5-Naphthalenedisulfonate)

“…The cleavage of the Sn−butyl group to afford 4 in very high yields, as observed in the present instance, is quite unusual. There are only a few scattered reports on Sn−alkyl cleavage reactions, leading to products in poor yields . It must be mentioned that the most common Sn−R cleavage reactions occur with benzyl- and allyltin compounds .…”

Difunctional distannoxanes, XR2SnOSnR2X

“…9 The dihydroxides R 4 Sn 2 (OH) 2 O usually spontaneously dehydrate to polymeric (R 2 SnO) n , but they can be isolated if they are sterically stabilised by a bulky group R, as in (HO) [(Me 3 Si) 2 CH] 2 SnOSn[CH(SiMe 3 ) 2 ] 2 (OH), 14 or HO(PhMe 2 CCH 2 ) 2 SnOSn(CH 2 CMe 2 Ph) 2 OH. 15 Dialkyltin oxides react with the appropriate amount of a strong acid, to give the the difunctional distannoxanes (Scheme 1, reaction c), for example, equation 5. 16 (5) Carboxylic acids give the dicarboxylates, (R'CO 2 ) R 2 SnOSnR 2 (OCOR'), and esters R'CO 2 R" give the alkoxy carboxylates, (R"O)R 2 SnOSnR 2 (OCOR').…”