847202-53-3Relevant academic research and scientific papers
Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H 7)2, with derivatives of the hexacarbonyls, M(CO) 6 (M = Cr, Mo, W)
Herberhold, Max,Liu, Jinnan,Milius, Wolfgang,Tok, Oleg,Wrackmeyer, Bernd
, p. 2438 - 2449 (2004)
Mononuclear carbonylmetal complexes of chromium, molybdenum and tungsten containing the sulfane S(C7H7)2 (1) have been obtained starting from precursors such as the THF-stabilized pentacarbonylmetal fragments, [M(CO)5](thf), the acetonitrile intermediates M(CO) 6-x(CH3CN)x (x = 1, 2, 3) (M = Cr, Mo, W) or the η4-norbornadiene complexes M(CO)4(C 7H8) (M = Cr, Mo). In addition to the pentacarbonyls, M(CO)5[S(C7H7)2] (M = Cr (2a), Mo (2b), W (2c)) which contain 1 unchanged as a two-electron sulfane ligand with two pending cyclohepta-2,4,6-trienyl substituents, isomeric complexes M(CO) 5[S(CH2Ph)(C7H7)] (M = Cr (3a), W (3c)) were obtained at higher temperatures (40-50°C) in which one of the two organic groups has been transformed into a benzyl substituent. In the tetracarbonyls, cis-M(CO)4[S(C7H7) (η2-C7H7)] (M = Mo (4b), W (4c)), the ligand 1 serves as an olefinic sulfane four-electron chelate ligand. The reaction of either Mo(CO)6 or (mesitylene)Mo(CO)3 with S(C7H7)2 (1) in boiling THF leads to the sulfur-free ditropyl complex Mo(CO)3[(η6-C 7H7)-C7H7] (5b, two isomers). The 1H and 13C NMR spectra of the new complexes 2-4 reveal various dynamic processes including pyramidal inversion of the sulfur atom and [1,7]-sigmatropic shifts at the C7H7 ring. The molecular structures of 2c, 3a, 4b and 4c have been determined by X-ray crystallography.
