216671-60-2Relevant academic research and scientific papers
Syntheses, Crystal Structures, Spectroscopic Characterization, and Electrochemical Studies of the Ditungsten(III) Complexes Cl3W (μ-L)3WCl3 and [Cl3W(μ-L)2 (μ-Cl)WCl3] (L = 1,4-Dithiane,1,4-Thioxane, pms = Pentamethylene Sulfide). C-S Bond Cleavage of the Bridging Thioether(s) in Cl3W (μ-L)3WCl
Boorman, P. Michael,Langdon, Naomi L.,Mozol, Vivian J.,Parvez, Masood,Yap, Glenn P. A.
, p. 6023 - 6029 (1998)
Reduction of WCl4 with 1 equiv of sodium amalgam, in the presence of either a refluxing toluene or neat solution of the desired thioether, produces a mixture of Cl3W(μ-L)3WCl3 (L = 1,4-dithiane (1), 1,4-thioxane (2), pms = pentamethylene sulfide (3)) and [Na][Cl3W(μ-L)2(μ-Cl)WCl3] (L = 1,4-dithiane (4), 1,4-thioxane (5), pms (6)). 4 and 5 could be converted to 1 and 2, respectively, in the presence of excess L in refluxing toluene. The structures of 1, 2, 3, 7, and 8 have been solved. 1, 2, and 3 are the first reported crystal structures for ditungsten-(III) tris-bridged cyclic thioether complexes. Crystal data are as follows: for an acetone solvate of 1, monoclinic space group P21ln (No. 14), a = 12.518(3) A?, b = 9,475(2) A?, c = 27.408(3) A?, β= 93.34(1)°, Z = 4; for an acetone solvate of 2, tetragonal space group P4/ncc (No. 130), a = 25.7603(3) A?, b = 25.7603(3) A?, c -18.6771(2) A?,Z= 16; for a hexane solvate of 3, monoclinic space group P21ln (No. 14), a = 11.874(4) A?, b = 21.823(3) A?, c = 12.545(3) A?, b = 100,46(3)°, Z = 4; for an acetonitrile solvate of 7, monoclinic space group P21/c (No. 14), a = 9.704(5) A?, b = 28.241(7) A?. c = 15.480(5) A?, β= 98.55(4)°, Z = 4; for a chloroform solvate of 8, monoclinic space group P21/a (No. 14), a = 13.531(4) A?, b = 25.207(5) A?, c = 14.083(3) A?, β= 115.57(2)°, Z = 4. 1, 2, and 3 were all shown to undergo C-S bond cleavage of a bridging thioether by reaction with [PPh4][Sptol] (ptol = 4-methyl phenyl) to afford the anionic complexes [PPh4][Cl3W(μ-S(CH2CH2) 2E)2(-μSCH2-CH2ECH 2CH2Sptol)WCl3] (E = S (9), O (10), CH2 (12)). 1, 2, 7, and 8 undergo reversible one-electron reductions.
