A New System in Organooxotin Cluster Chemistry Incorporating Inorganic and Organic Spacers between Two Ladders Each Containing Five Tin Atoms

Abstract

Hydrolysis of dibenzyltin dichloride in ethanol has been found to give an unprecedented carbonate anion (CO(3) (2-))-bridged double-ladder organooxotin cluster, [(R(2)SnO)(3)(R(2)SnOH)(2)(CO(3))](2) (1, R = C(6)H(5)CH(2)), with five tin atoms in each ladder. With the aim of obtaining organooxotin clusters with large cavities suitable for host-guest chemistry, we used 1,1'-ferrocenedicarboxylic acid (H(2)L(a)) and hexanedioic acid (H(2)L(b)) to replace the carbonate anions (CO(3) (2-)), and thereby clusters [(R(2)SnO)(3)(R(2)SnOH)(2)L(a)](2) (2) and [(R(2)SnO)(3)(R(2)SnOH)(2)L(b)](2) (3) were obtained. When 1 was treated with benzoic acid (HL(c)) in different stoichiometric ratios (1:4, 1:10), ladder cluster (R(2)SnO)(3)(R(2)SnOH)(2)(L(c))(2) (4) and drum cluster [RSn(O)L(c)](6) (5) were obtained. Through the hydrolysis of Cy(2)SnCl(2) (Cy = C(6)H(11)) and (C(6)H(5)CH(2))(2)SnCl(2), two interesting ethanolate-modified clusters [Cy(2)(C(2)H(5)O)SnOSn(C(2)H(5)O)Cy(2)](2) (6) and [(R(2)SnO)(3)(R(2)SnOH)(R(2)SnOC(2)H(5))(CO(3))](2) (7) were obtained. All the tin atoms in these ladder clusters are five-coordinate surrounded by two alkyl groups and three O atoms, and have distorted trigonal-bipyramidal coordination environments with two carbon atoms and one O atom in the equatorial positions and two O atoms in the axial positions. The structures of all these compounds have been established by single-crystal X-ray diffraction analyses.

Imine-functionalized, fluorescent organomercury and -tellurium compounds

“…Cyclophosphazenes and organostannoxanes have, for example, been used as scaffolds to support a variety of interesting groups that are electrochemically or photochemically active [2,3]. Organostannoxanes containing photoactive substituents have been shown to possess interesting photochemical behavior in solution as well as in the solid state [3][4][5][6][7]. Such a methodology has not yet been applied to the realm of organotellurium chemistry.…”

Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions

“…The crystallization of 2 from hot toluene gave rise, upon slow cooling, to air-stable colorless crystals characterized as 2·6 (C 7 H 8 ) by an X-ray crystallographic analysis. In the past, Ma and co-workers reported the isolation of 2·2CH 3 COCH 3 , obtained from dibenzyltin dichloride when it was kept in the presence of atmospheric CO 2 , with 15 % yield [21]. The synthetic pathway described here involving the use of sealed vial conditions increases the yield significantly up to 44 %.…”

“…2). From a structural point of view, the double coplanar ladder-type structure constitutes a remarkable feature, up to now exclusively Brought to you by | MIT Libraries Authenticated Download Date | 5/9/18 6:55 PM observed in the case of di-n-butyl-and dibenzyltin oxo clusters [19,21,22]. (2) toward trifluoromethanesulfonic acid (TfOH) Numerous examples of trifluoromethanesulfonate derivatives have been reported previously in organotin(IV) chemistry and structurally characterized by single-crystal X-ray diffraction [23].…”

“…2). From a structural point of view, the double coplanar ladder-type structure constitutes a remarkable feature, up to now exclusively observed in the case of di-n-butyl-and dibenzyltin oxo clusters [19,21,22]. …”

Synthesis and Characterization of Archetypal Ladder-Like Dibutyloxotin Cluster Derived from Sterically Encumbered 4-[(E)-2-(4-hydroxy-5-methylphenyl)-1-diazenyl]benzoate

“…In addition, a variety of organooxotin clusters, such as ladder, drum, cube, O-capped and football cage (Scheme 1) have been prepared and characterized by X-ray diffraction analyses [3][4][5]. More examples of organooxotin clusters, such as alkyl-bridged double-and triple-ladder clusters [6,7], as well as alkyl-bridged Sn 3 O 3 cluster [8], double O-capped clusters [9], organooxotin clusters bridged by an inorganic moiety [10] and organooxotin cluster containing a Sn 5 O 5 ladder [11], are reported in the literature. Among organooxotin clusters, diorganotin clusters of the type {[R 2 Sn(L)] 2 O} 2 were investigated in detail and only a few examples of such complexes with bulkier ligands with flexible diazenyl group have been reported, e.g.,{[Bu 2 Sn(O 2 CC 6 H 4 (OH-2)(N=NC 6 H 4 (X)-5))] 2 O} 2 (X=H, 4-CH 3 , 4-Cl, 4-Br) [12] and {[Oct 2 Sn(O 2 CC 6 H 4 (OH-2)(N=NC 6 H 4 (X)-5))] 2 O} 2 (X=2-OCH 3 , 3-CH 3 ) [13].…”