82247-31-2Relevant academic research and scientific papers
η2-Alkoxythiocarbonyl and Chelating Ph2PCH=C(R)S-Ligands via Intramolecular Coupling of Co-ordinated CS2 and Ph2PCCR; X-Ray Crystal Structure of Fe(CO)t)S>
Carty, Arthur J.,Hartstock, Fred,Taylor, Nicholas J.,Bozec, Hubert Le,Robert, Paul,Dixneuf, Pierre H.
, p. 361 - 363 (1980)
Reaction of η2-CS2 complexes, Fe(CS2)(CO)2(L1)(L2) with a phosphino-alkyne Ph2PCCBut in alcohols, generates, via intramolecular coupling and CS2 fragmentation, novel derivatives containing η2-alkoxythiocarbonyl and chelating Ph2PCH=C(But)S-ligands; Fe(CO)t)S> has been characterised by X-ray diffraction.
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.
