82264-89-9Relevant academic research and scientific papers
Reactions of iron(II) complexes modulated by the unsymmetrical chelating alkenethiolato-phosphine ligand. Elaboration of a novel carbenethiolato-phosphine tripodal ligand. X-ray structure determinations of [Fe(η2-Ph2PCH2C(t-Bu)=S)(η 2-SCOMe)(PPh3)(CO)](PF6) and ClFe[η3-Ph ...
Samb, Abdoulaye,Demerseman, Bernard,Dixneuf, Pierre H.,Mealli, Carlo
, p. 26 - 33 (2008/10/08)
Full title: Reactions of iron(II) complexes modulated by the unsymmetrical chelating alkenethiolato-phosphine ligand. Elaboration of a novel carbenethiolato-phosphine tripodal ligand. X-ray structure determinations of [Fe(η2-Ph2PCH2C(t-Bu)=S)(η 2-SCOMe)(PPh3)(CO)](PF6) and ClFe[η3-Ph2PCH2C(t-Bu)(S)(SCOMe)](PPh 3)(CO) complexes. Protonation of neutral complexes Fe(η2-Ph2PCH=C(R)S)(η2-SCOMe)(PPh 3)(CO) (1a, R = t-Bu; 1b, R = Ph) with HBF4 and HPF6 occurs reversibly at the chelating Ph2PCH=C(R)S- anionic ligand to give the cationic derivatives [Fe(η2-Ph2PCH2C(R)=S)(η 2-SCOMe)(PPh3)(CO)]+ (2, 3). With HCl or HBr and 1a, the coordination of the halide and further intramolecular coupling of the sulfur-containing groups take place to afford a novel tripodal ligand in XFe[η3-Ph2PCH2C(t-Bu)(S)(SCOMe)](PPh 3)(CO) (5, X = Cl; and 6, X = Br). When the same reaction is performed in the presence of water, the formal replacement of the SCOMe group by CO and Cl ligands affords ClFe(η2-Ph2PCH=C(t-Bu)S)(PPh3)(CO) 2 (7). Complexes 1a and 1b react with trimethylphosphine to give the η1-C(OMe)=S derivatives Fe(η2-Ph2PCH=C(R)-S)(η 1-C(OMe)=S)(PMe3)2(CO) (8a,b) which on protonation with HBF4 or HCl undergo methanol elimination and formation of cationic iron thiocarbonyl complexes [Fe(η2-Ph2PCH=C(R)S)(PMe3) 2(CO)(CS)]+ (10, 11). The crystal structures of the compounds [Fe(η2-Ph2PCH2C(t-Bu)=S)(η 2-SCOMe)(PPh3)(CO)](PF6) (3a) and ClFe[η3-Ph2PCH2C(t-Bu)(S)(SCOMe)](PPh 3)(CO) (5) have been determined. Crystal data for 3a are as follows: a = 18.969 (6) A?, b = 10.779 (4) A?, c = 9.183 (4) A?, α = 69.10 (3)°, β = 85.73 (2)°, γ = 82.87 (2)°, triclinic P1, Z = 2, R = 0.062. Crystal data for 5 are as follows: a = 15.213 (7) A?, b = 20.969 (7) A?, c = 13.083 (6) A?, β = 99.44 (3)°, monoclinic, P21/n, Z = 4, R = 0.073. The structure of 3a has the pseudooctahedral geometry of a d8 L4M system, η2 coordinated by a heteroallene group. The structure of 5 shows that the metal atom is six-coordinate, using three donor atoms (P, S, and C) of the newly formed tripodal ligand Ph2PCH2C(t-Bu)(S)(SCOMe) together with chloride, CO, and PPh3.
