78791-00-1Relevant articles and documents
Chemistry of η2-CS2 metal complexes: Synthesis of dithiolene complexes of iron via acetylene additions to Fe(η2-CS2)(CO)2(PR3) 2. X-ray structure of Fe[S2C(COMe)C(C6H4NO 2)](CO)[P(OMe)3]2
Carty, Arthur J.,Dixneuf, Pierre H.,Gorgues, Alain,Hartstock, Frederick,Le Bozec, Hubert,Taylor, Nicholas J.
, p. 3929 - 3934 (2008/10/08)
The synthesis of a series of (dithiolato)iron carbonyl complexes Fe[S2C(Z1)C(Z2)](CO)L1L 2(L1L2 = PMe3, P(OMe)3) via the reaction of unsymmetrical, activated acetylenes Z1-C≡C-Z2 with the η2-CS2 complexes Fe(η2-CS2)(CO)2L1L2 is described. These compounds have been characterized by microanalysis, infrared spectroscopy, and 1H, 31P, and 13C NMR as well as mass spectroscopy. Crystals of a typical derivative Fe[S2C(COMe)C(C6H4NO 2)](CO)[P(OMe)3]2 are monoclinic, space group P21/n with a = 8.176 (1) A?, b = 29.308 (3) A?, c = 11.021 (1) A?, β = 99.06 (1)°, Z = 4, ρm = 1.50 g cm-3, and ρc = 1.494 g cm-3. The structure was solved by Patterson and Fourier methods using 2591 observed (I ≥ 3σ(I)) intensities measured on a Syntex P21 diffractometer. Refinement by full-matrix least-squares methods gave R and Rw values of 0.031 and 0.042. The iron atom stereochemistry is best described as distorted trigonal bipyramidal with apical positions occupied by one sulfur atom of a dithiolate ligand and a trans carbonyl group. The remaining dithiolate sulfur atom occupies an equatorial site; two phosphite phosphorus atoms are also equatorial. The structure thus differs substantially from those of square-pyramidal α- and β-Ru[S2C2(CF3)2](CO)(PPh 3)2. The method of synthesis that involves 1,3-dithiocarbene complexes as intermediates is a useful route to unsymmetrical carbonyl dithiolates.
