Synthesis and structure of diorganotin dibromides, R2SnBr2 (R = 2,4,6-trimethylphenyl or 2,4,6-trimethylbenzyl): Hydrolysis of (2,4,6-Me3C6H2)2SnBr2

Abstract

The reaction of SnBr 4 with in situ generated 2,4,6-trimethylphenylmagnesium bromide afforded a mixture of (2,4,6-Me 3 C 6 H 2 ) 2 SnBr 2 (1) and (2,4,6-Me 3 C 6 H 2 ) 3 SnBr (2) which could be separated from each other by their solubility differences in diethyl ether. On the other hand, the reaction of tin metal with 2,4,6-Me 3 C 6 H 2 CH 2 Br afforded (2,4,6-Me 3 C 6 H 2 CH 2 ) 2 SnBr 2 (3). Hydrolysis of the latter using triethylamine as the base afforded [{(2,4,6-Me 3 C 6 H 2 CH 2 ) 2 Sn} 2 (μ-O)(Br)(μ-OH)] 2 ⋅2CH 2 Cl 2 (4) while the use of NaOH as the base afforded [{(2,4,6-Me 3 C 6 H 2 CH 2 ) 2 Sn} 2 (μ-O)(OH)(μ-OH)] 2 ⋅2CH 2 Cl 2 (5). Compounds 4 and 5 are dimeric tetraorganodistannoxanes consisting of a central distannoxane (Sn 2 O 2 ) motif.

Dibromodiphenylstannane: isolated centrosymmetric dimers as a new structure motif for the intermolecular association of diorganotin(IV) dihalides

“…In the solid state, diorganotin(IV) dichlorides, dibromides and diiodides with large organic residuals like tert-butyl ( t Bu 2 SnCl 2 ; Dakternieks et al, 1994), 2-methyl-2-phenylpropyl [(MePhPr)PhSnBr 2 ; Bomfim et al, 2003] or mesityl (Mes 2 -SnBr 2 ; Chandrasekhar & Thirumoorthi, 2010) are monomeric also, with large respective carbon and small halide opening angles, viz. 133.1 (2) and 101.86 (5) in t Bu 2 SnCl 2 , 127.0 (1) and 102.18 (1) in (MePhPr)PhSnBr 2 , and 118.7 (2) and 100.51 (2) in Mes 2 SnBr 2 .…”

Organotin Phosphates Assembled from a Sterically Hindered Organophosphate, ArOP(O)(OH)2, (Ar = 2,6-(CHPh2)2-4-i-Pr-C6H2): Syntheses and Structures

“…The structural diversity of organooxotin compounds is extremely impressive and is achieved by surprisingly simple reactions involving an organotin precursor (organotin chlorides, -oxides, -hydroxides, and -oxide-hydroxides) and an appropriate protic acid (carboxylic acids, phosphinic acids, sulfonic acids, phosphonic acids, and phosphoric acid monoester). − Among the phosphorus-based acids, interestingly, phosphinic [R 2 P­(O)­(OH)] and phosphonic acids [RP­(O)­(OH) 2 ] have received much greater attention than phosphates [ROP­(O)­(OH) 2 ]. − On the other hand, it is well-known that the P–O linkage in phosphates makes these ligands more flexible because of the hinge oxygen atom compared to many phosphonic acids where the phosphorus atom is directly linked to the organic unit . Indeed, previous studies on the reactions of phosphates with organotin substrates, though sparse, have already revealed significant structural variation .…”

“…Such a coordination action leads to the formation of a 16-membered macrocycle. In contrast to(2), in(3), each of the four tin centers is further connected to another trimethyltin motif, thus increasing its nuclearity. Finally, the reaction of LH 2 with Me 3 SnCl in a 1:2 stoichiometric ratio afforded a onedimensional coordination polymer, [Me 3 Sn(LH)] n •nCH 3 OH (4).…”