Coordination Behavior and Transformations of Thienyl-Substituted Diacetylenes upon Coordination to Os₃H₂(CO)₁₀

Abstract

The reaction between 2 and 3thienyl substituted 1,3butadiynes and the electron deficient osmium cluster Os 3 H 2 (CO) 10 yields trinuclear coordination products, associated with transformations of the diacetylene ligands. Depending on the heteroaryl end groups, osmium clusters with both closed and 1 open Ostriangle core were formed. The reaction between Os 3 H 2 (CO) and 1,4bis(2thienyl)butadiyne yielded [Os 3 (µH)(CO) 10 {(µη(C 4 H 3 S)(C 8 H 4 S)}] (1) and [Os 3 (µH)(CO) {(µ 3 η 2 η 1 η 1 (SC 7 H 4)C(SC 4 H)}] (2) whereas in the analogous case of 1,4bis(3thienyl)butadiyne the main coordination product was found to be [Os 3 (µH)(CO) 10 {(µη(C 4 H 3 S)(C 8 H 4 S)}] (3). Compounds 13 were stable in air, but lost carbon monoxide upon prolonged heating. Thermal decarbonylation of 1 under N 2 yielded a mixture of [Os 3 (µH)(CO) 9 {(µ 3 η 3 (C 4 H 3 S)(C 8 H 4 S)}] (4) and [Os 3 (µH) 2 (CO) 9 {(µ 3 η 1 η 1 (C 4 H 3 S)(C 8 H 3 S)}] (5). Thermal decarbonylation of 2 yielded [Os 3 (µH)(CO) 9 {(µ 3 η 3 (C 4 H 3 S)(C 8 H 4 S)}] (6), while thermal decarbonylation of 3 yielded [Os 3 (µH)(CO) 9 {(µ 3 η 3 (C 4 H 3 S)(C 8 H 4 S)}] (7). A reaction involving 3 with CF 3 COOH affords as the main cluster product the known cluster [Os 3 (µH)(CO) 10 (O 2 CF 3)] (8) and, unusually, permits the isolation and characterisation of the novel organic molecule [(C 4 H 3 S)(C 8 H 4 S)(OCF 3)] (9) cleaved from the parent cluster. The structures of the new compounds were established by single crystal Xray studies and spectroscopic methods, and supported by density functional theory.

Facile one-pot, multi-component reaction to synthesize spirooxindole-annulated thiopyran derivatives under environmentally benevolent conditions

“…Among the S -containing heterocyclic compounds, thiopyran scaffolds have been carefully examined by scientists, and studies have validated their notable features, such as antiviral and antimicrobial properties. Moreover, one of the striking features of these motifs is their application in the treatment of cancer [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. In consequence, chemists are hunting new ways to create various thiopyran-containing heterocycles.…”

Application of Nanomagnetic NH 2 .MIL-101(Fe)/ED as a Retrievable and Efficient Catalyst for the Synthesis of 2,6-Diamino-4-Aryl-4H-Thiopyran- 3,5- Dicarbonitrile Derivatives

“…[6][7][8][9][10][11][12][13] Among the S-heterocycles, thiopyran frameworks are known as maneuverable skeletons and therefore have been subject to extensive study due to their unique properties such as the anticancer, and antimicrobial activities. [14][15][16][17][18][19][20][21][22][23] Meanwhile, tricyclic thiopyran-2-one compounds are of use in the therapies for the treatment of viral infections and diseases including AIDS which further emphasize that these organic skeletons are likely to be of considerable practical signi cance. 24 Hence, chemists are hunting new ways to create various S-heterocycles and therefore a great deal of synthetic ways have been developed for the construction of these structures.…”