C, N-Chelated organotin(iv) azides: synthesis, structure and use within click chemistry. (15th March 2016)

• Record Type: Journal Article
• Authors: Švec, Petr; Bartoš, Karel; Růžičková, Zdeňka; Cuřínová, Petra; Dušek, Libor; Turek, Jan; De Proft, Frank; Růžička, Aleš
• Is Part Of: New journal of chemistry. Volume 40:Number 7(2016:Jul.)
• Page Start: 5808
• Page End: 5817
• Publication Date: 2016-03-15
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c5nj03187g
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Novel organotin(iv ) azides were employed as building blocks to prepare various organotin(iv ) tetrazolides or triazolides. Abstract : A set of tri- and diorganotin(iv ) azides bearing 2-( N, N -dimethylaminomethyl)phenyl as a C, N-chelating ligand (L CN ) has been prepared and structurally characterized. Triorganotin(iv ) azides of the type L CN R2 SnN3 (R = n -Bu (1 ) and Ph (2 )) and (L CN )2 ( n -Bu)SnN3 are monomeric both in solution and in the solid state. The central tin atom in these species is five-coordinated with distorted trigonal bipyramidal geometry. Diorganotin(iv ) azides of the type L CN RSn(N3 )2 (R = n -Bu and Ph) are monomeric with trigonal bipyramidal geometry around the tin atom as well. Finally, (L CN )2 Sn(N3 )2 contains a six-coordinated tin atom with heavily distorted octahedral geometry due to the presence of two L CN units. The potential use of selected organotin(iv ) azides1 and2 as useful building blocks within click chemistry was investigated. The reactions of1 and2 with various nitriles resulted in the formation of corresponding triorganotin(iv ) tetrazolides ( i.e. κ -N 1 : L CN ( n -Bu)2 Sn(5-MeCN4 ), L CN Ph2 Sn(5-MeCN4 ), L CN ( n -Bu)2 Sn(5-Me2 NCH2 CN4 ), L CN Ph2 Sn(5-Me2 NCH2 CN4 ); and κ -N 2 : L CN ( n -Bu)2 Sn(5- t -BuCN4 ), L CN Ph2 Sn(5- t -BuCN4 ), L CN ( n -Bu)2 Sn(5-PhCN4 ), L CN Ph2 Sn(5-PhCN4 )). Similarly, the reaction of1 and2 with cyclooctyne provided corresponding C, N-chelated di- n -butyl/diphenyltin(iv ) κ -N 1 4, 5, 6, 7, 8, 9-hexahydrocycloocta[ d ][1, 2, 3]triazol-1-ides. All azido complexes and products of the [3+2] cycloaddition reactions were characterized by the combination of elemental analysis, mass spectrometry, IR spectroscopy, multinuclear NMR spectroscopy and, in the case of crystalline materials, XRD analysis. In addition, DFT calculations were carried out within the click chemistry reactions in order to corroborate the preferred formation of the respective tetrazolide regioisomer.