126111-52-2Relevant academic research and scientific papers
Reaction of organoisothiocyanates with [Co(η-C5H5)(PPh3)2]. Preparation, structure, and reactivity of trinuclear cobalt complexes containing a triply bridging, two-electron-donor CNR ligand
Cullen, E. Patricia,Fortune, John,Manning,McArdle, Patrick,Cunningham, Desmond,Stephens, Frederick S.
, p. 1443 - 1448 (2008/10/08)
The slow addition of RNCS to [Co(η-C5H5)(PPh3)2] in benzene at room temperature gives a good yield of green [Co3(η-C5H5)3(μ 3-S)(μ3-CNR)] (1) where R = alkyl or aryl. A crystal structure determination (R = Et; monoclinic, space group P21/c with a = 14.405 (4) A?, b = 9.221 (3) A?, c = 15.040 (5) A?, β = 117.9 (3)°, and Z = 4) shows that these complexes contain a planar Co3(η-C5H5)3 triangle (Co-Co = 2.447, 2.452, and 2.483 (1) A?) capped on one side by a μ3-S atom and on the other by a μ3-CNR ligand acting as a two-electron donor through C. The CNEt ligand is bent at N so that the N-Et bond lies above the center of one Co-Co bond with a C-N-Et angle of 129°. The N atoms of 1 are basic, but the basicity is a function of R. When R = Me or Et (1) reacts with [Ph3C]BF4 to give [Co3(η-C5H5)3(μ3-S){μ 3-CN(H)R}]BF4, [2]BF4, although the source of the protons is unclear, and with MeI or R′SO3CF3 to give [Co3(η-C5H5)3(μ 3-S){μ3-CN(R′)R}]X, [3]X; both [2]BF4 and [3]X react with excess HBF4·OEt2 to give [Co3(η-C5H5)3(μ 3-S){μ3-CN(H)2R}][BF4] 2, [4][BF4]2, and [Co3(η-C5H5)3(μ 3-S){μ3-CN(H)(R′)R}][BF4]2, [5][BF4]2 salts, respectively. In contrast, when R = aryl, both [Ph3C]BF4 and excess HBF4·OEt2 convert 1 to [2][BF4] only, and some 1 molecules are not alkylated to [3]I by MeI, but all are alkylated by MeSO3CF3. Infrared and NMR spectroscopic data are reported and discussed.
