Oxygen- and Sulfur-Capped Organotin Clusters

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

“…4f), and which suggests an increase of the coordination number of the tin atoms from five to six. (C 7 H 7 Sn) 6 …”

“…Since then, the inventory of structures has regularly been updated; it reveals a profuse structural diversity [2]. Indeed, on the basis of X-ray crystallographic studies, a great variety of shapes has already been identified for organotin-oxo derivatives which include prismane [3], butterfly [4], ladder [5], O-and Scapped cluster [6], drum [7], cube [8], double cube [9], football cage [10], crown [11], extended cage [12], and coordination polymer types [13]. Moreover, the structural interrelationship between these polynuclear arrangements has been clearly established, highlighting possible mechanisms of interconversion from one form to another [14].…”

“…perimental protocol, we report herein the synthesis of ((PhCH 2 ) 2 SnO) 6 [((PhCH 2 ) 2 SnOH) 2 (CO 3 )] 2 (2), from (PhCH 2 ) 2 SnO (1) used as a tin precursor. The crystal structure of 2·6C 7 H 8 (C 7 H 8 = free toluene molecules), as determined by single crystal X-ray diffraction, as well as the solution multinuclear NMR characterization are presented.…”

“…To our knowledge, the hexa-and undecanuclear frameworks of 3 and 4, respectively, are unusual and have never been reported previously in the literature on organotin(IV) oxo clusters. (2) The reaction of dibenzyltin oxide, (PhCH 2 ) 2 SnO (1), with dimethyl carbonate in a sealed vial at 125 • C in the presence of toluene and traces of methanol provides the polynuclear dibenzyltin(IV) oxo cluster, ((PhCH 2 ) 2 SnO) 6 [((PhCH 2 ) 2 SnOH) 2 (CO 3 )] 2 (2). 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.…”

“…Formerly, investigating the direct synthesis of organic carbonates from carbon dioxide and alcohols promoted by organometallic tin(IV) precursors [18], and during recycling experiments, we isolated a deca(organotin(IV)) oxo cluster, characterized as (nBu 2 SnO) 6 [(n-Bu 2 SnOCH 3 ) 2 (CO 3 )] 2 and arranged in a pair of coplanar [(n-Bu 2 Sn) 5 O] 5 ladders bridged by two carbonate groups ( Fig. 1) [19].…”