82247-29-8Relevant 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.
Chemistry of η2-CS2 complexes. Mononuclear iron compounds containing alkoxythiocarbonyl and chelating Ph2PCH=C(R)S ligands via coupling of coordinated CS2 and phosphlnoacetylenes: X-ray structure of Fe(CO)[P(OMe)3][Ph2PCH=C(t-Bu)S][CS(OMe)]
Robert, Paul,Bozec, Hubert Le,Dixneuf, Pierre H.,Hartstock, Frederick,Tayior, Nicholas J.,Carty, Arthur J.
, p. 1148 - 1154 (2008/10/08)
Intramolecular coupling reactions involving the ligands CS2 and Ph2PC≡CR held proximate in the coordination sphere of a mononuclear iron carbonyl complex have been explored. Reaction of Fe2(CO)9 with the phosphinoacetyiene Ph2PC≡C-t-Bu in CS2 solution affords tran-Fe(η2-CS2)(CO)2(Ph 2PC≡C-t-Bu)2. In MeOH under reflux Fe(η2-CS2)(CO)2(Ph2(Ph 2PC≡C-t-Bu)2 is converted to the complex Fe(CO)(Ph2PC= Ph2PC≡C-t-Bu)[Ph2PCH=CS(t-Bu)][CS(OMe)] which contains novel, chelating Ph2PCH==CS(t-Bu) and η2-CS-(OMe) ligands. Similarly trans-Fe(η2-CS2)(CO)2(L1)(L 2) (L1, L2 = tertiary phosphine or phosphite) in the presence of phosphinoalkyne Ph2PC=CR (R = Ph, t-Bu) in raethanol are converted to Fe(CO)(L1)-[Ph2PCH=CS(R)][CS(OMe)]. Correspondingly Fe(η2-CS2)(CO)2(PPh3)(PMe 2Ph) in CH2Cl2 reacts with EtSH and Ph2PC≡C-t-Bu to afford Fe(CO)(PMe2Ph)[Ph2PCH=C(S)-t-Bu] [CS(SEt)]. These compounds were characterized by microanalysis, 1H, 31P, and 13C NMR spectroscopy, and mass spectroscopy. Single crystals of the title compound Fe(CO)[P(OMe)3][Ph2PCH=CS(t-Bu)][CS(OMe)] are triclinic of space group PI with a = 11.115 (1) A?, b = 11.347 (1) A?, c = 12.882 (1) A?, a = 97.80 (1)°, β= 64.90 (1)°, 7 = 83.97 (1)°, and Z = 2. The structure was solved and refined to R = 0.042 and R = 0.051 on the basis of 2647 independent Syntex P21 measured reflections (Mo Kα radiation). The stereochemistry of the iron atom is pseudo square pyramidal with an axial CO group, the phosphorus, and sulfur atoms of the chelating PS ligand, the phosphite phosphorus atom, and the carbon atom of the η2-CS(OMe) group forming an approximate square plane. The sulfur atom S(2) of the C(S)OMe group also interacts with the iron atom. Likely mechanisms for these novel reactions are discussed. The synthetic route has potential for the generation of rigid, chelating PS ligands.
