211446-68-3Relevant academic research and scientific papers
4-Iodobenzylidyne as a precursor ligand for extended unsaturated alkylidyne ligands
Yu, Marie Pui Yin,Cheung, Kung-Kai,Mayr, Andreas
, p. 2373 - 2378 (1998)
The synthesis of the 4-iodobenzylidyne and 4-bromobenzylidyne tungsten complexes [W(CC6H4Z-4)X(CO)2-(pic)2] [Z = I; X = Cl, (3a), Z = I, X = Br (3b); Z = Br, X = Cl (4a)] was achieved by sequential reaction of [W(CO)6] with Li[C6H4I-4] or Li[C6H4Br-4] in diethyl ether and C2O2Cl2 or C2O2Br2 and 4-picoline (pic, 4-methylpyridine) in CH2Cl2. The chloro ligand in 3a could be replaced by the iodo ligand to give 3c (X = I) by reaction with NaI in THF. Substitution of the picoline ligands by N,N,N′,N′-tetramethylethylenediamine (tmeda) and dppe afforded the complexes [W(CC6H4Z-4)X(CO)2(L2)] [Z = I, L2 = tmeda, X = Cl (5a), X = Br (5b), X = I (5c); Z = Br, L2 = tmeda, X = Cl (6a); Z = I, L2 = dppe, X = Cl (7a), X = Br (7b), X = I (7c)]. The iodo group of the new alkylidyne complexes underwent PdII catalyzed cross-coupling reactions effectively. Thus coupling of complexes 5a with trimethylsilylacetylene, followed by hydrolysis, afforded the acetylide derivative [W{CC6H4(CCH-4)}-Cl(CO)2(tmeda)], 8. The alkynyl derivatives [W {CC6H4(CCC6H4Y)-4}Cl(CO) 2(tmeda)] (Y = H 9, CHO 10 or CN 11) were obtained by reactions of complex 5a with the respective aromatic acetylenes. The molecular structures of complexes 5a and 10 have been determined by X-ray crystallography.
