38894-55-2Relevant academic research and scientific papers
Microwave synthesis of benchmark organo-iron complexes
Garringer, Sean M.,Hesse, Andrew J.,Magers, John R.,Pugh, Kristapher R.,O'Reilly, Stacy A.,Wilson, Anne M.
, p. 6841 - 6844 (2010/04/01)
Microwave-assisted reaction techniques have been applied to the formation of a variety of organo-iron species. The species synthesized include ferrocene and acetyferrocene, piano stool complexes such as CpFe(CO)2I, CpFe(PPh3)(CO)I, a
The reaction of M(CO)3(Ph2PCH2CH 2PPh2) (M = Fe, Ru) with parahydrogen: Probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products
Schott, Daniele,Callaghan, Philip,Dunne, John,Duckett, Simon B.,Godard, Cyril,Goicoechea, Jose M.,Harvey, Jeremy N.,Lowe, John P.,Mawby, Roger J.,Mueller, Georg,Perutz, Robin N.,Poli, Rinaldo,Whittlesey, Michael K.
, p. 3218 - 3224 (2007/10/03)
The photochemical reaction of Ru(CO)3(dppe) and Fe(CO) 3(dppe) (dppe = Ph2PCH2CH2PPh 2) with parahydrogen has been studied by in situ-photochemistry resulting in NMR spectra of Ru(CO)2(dppe)(H)2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)2(dppe)(H)2. This effect is associated with a singlet electronic state for the key intermediate Ru(CO)2(dppe) while Fe(CO)2(dppe) is a triplet. DFT calculations reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO) 2(dppe)(H)2 and Fe(CO)2(dppe)(H)2 has been examined by NMR spectroscopy and rationalised by theoretical methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centres interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local minimum (intermediate) was found along the rearrangement pathways.
Lewis base stabilized transition metal complexes of divalent silicon species
Chauhan, Bhanu P. S.,Corriu, Robert J. P.,Lanneau, Gérard F.,Priou, Christian,Auner, Norbert,Handwerker, Hermann,Herdtweck, Eberhardt
, p. 1657 - 1666 (2008/10/09)
A direct photochemical synthesis of silanediyl-iron tetracarbonyl complexes Ph2Si(B)=Fe-(CO)4 [B = 1,3-dimethylimidazolidinone (DMI) or hexamethylphosphoric triamide (HMPA)] is described. The Lewis base character of DMI is strong eno
Enthalpies of reaction of (diene)- and (enone)iron tricarbonyl complexes with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the L2Fe(CO)3 complexes
Luo, Lubin,Nolan, Steven P.
, p. 2410 - 2415 (2008/10/08)
The enthalpies of reaction of (BDA)Fe(CO)3 (BDA = (C6H5)CH=CHO(CH3), benzylideneacetone) with a series of mono- and multidentate ligands, leading to the formation of (η4-L)Fe(CO)3, (L′)2Fe(CO)3, and (L″)Fe(CO)3 complexes (L = diene, enone; L′ = monodentate arsines; L″ = bidentate ligands), have been measured by solution calorimetry in THF at 50°C. The range of reaction enthalpies spans some 44 kcal/mol. The overall relative order of stability established is as follows: for monodetate ligands, AsPh3 3 a relative order of complex stability for these compounds in the iron tricarbonyl system. These data allow the calculation of the enthalpy associated with the geometric isomerization process (axial-equatorial/ diaxial) present in the (L′)2Fe(CO)3 system (5.4 ± 0.5 kcal/mol) as well as for a quantitative analysis of ring strain energies in the (L″)Fe(CO)3 system. The four-membered metallacycle is the only cyclic structure exhibiting significant strain energy (12.6 kcal/mol). Comparisons with other organometallic systems and insight into factors influencing the Fe-L bond disruption enthalpies are also discussed.
Calorimetric studies of the heats of protonation of the metal in Fe(CO)3(bidentate phosphine, arsine) complexes: Effects of chelate ligands on metal basicity
Sowa Jr., John R.,Zanotti, Valerio,Facchin, Giacomo,Angelici, Robert J.
, p. 160 - 165 (2007/10/02)
Titration calorimetry has been used to determine the beats of protonation (ΔHHM) of Fe(CO)3(LL) complexes (LL = dppm, dppe, dppp, dppb, dppbz, cis-dppv, arphos, dmpm, dcpe, and diars) with CF3SO3H in 1,2-dichlor
REDUCTIVE CARBONYLATION OF IRON(II) WITH MANGANESE METAL. PREPARATION OF CARBONYL DIPHOSPINE COMPLEXES OF IRON(0)
Battaglia, Luigi Pietro,Chiusoli, Gian Paolo,Delledonne, Daniele,Nardelli, Mario,Pelizzi, Corrado,Predieri, Giovanni
, p. 345 - 348 (2007/10/02)
A slective one-step method is reported for the synthesis of Fe(CO)3(P-P) derivatives (P-P = chelating tertiary diphosphine), starting from FeCl2, diphosphine and manganese, in tetrahydrofuran, under a CO atmosphere, at room temperature.The use of manganese metal as reducing agent is essential for the selectivity of the process.In the absence of the reducing agent, complexes of the type Fe(CO)2(P-P)Cl2 have been obtained.All these iron compounds have been characterized by IR and 31P NMR spectroscopy.
Transition-Metal Silyl Complexes, 18. - Hydrido-Silyl and Bissilyl Complexes of Iron with Bridging or Chelating Diphosphinoethane Ligands
Knorr, Michael,Mueller, Johannes,Schubert, Ulrich
, p. 879 - 888 (2007/10/02)
Complexes 2(dppe) (1) (dppe = Ph2PCH2CH2PPh2), 2(dppe) (2), (CO)2(dppe)Fe(H)SiR3 (3), and (CO)2(dppe)Fe(SiR3)2 (6) are synthetized by several routes: by photochemical reaction of dppe-substituted iron carbonyls with HSiR3, by thermal reaction of (CO)4Fe(H)SiR3 or (CO)4Fe(SiR3)2 with dppe, or by exchange of the silyl groups.The dinuclear complexes 1 and 2 can be converted to the mononuclear complexes 3 and 6.The choice of the most suitable method of preparation depends essentially on the nature of the silyl ligand.Bissilyl complexes (2 or 6) are only obtained if SiR3 = SiCl3 or SiMeCl2.In solution the complexes 3 are fluxional.In the crystalline state 3d (SiR3 = SiMe3) shows a distorted octahedral geometry.The silyl group has trans orientation to one of the phosphorus atoms and cis to the hydride ligand, which in turn is trans to one of the carbonyls.
The crystal and molecular structure of tricarbonyliron(0)
Battaglia, Luigi P.,Delledonne, Daniele,Nardelli, Mario,Pelizzi, Corrado,Predieri, Giovanni,Chiusoli, Gian Paolo
, p. 101 - 114 (2007/10/02)
tricarbonyliron(0), Fe(CO)3-(Ph2PCH2CH2PPh2), has been prepared by reducing FeCl2 with metallic manganese under an atmosphere of CO in the presence of the diphosphine at room temperature in THF.The results of an X-ray diffraction study (room temperature, Mo-Kα) are: P21/n, a 12.260(6), b 15.890(7), c 14.227(6) Angstroem, β 110.57(3) grad, Z = 4, Dc 1.378, Dm 1.40 Mg m-3, RF(2957/413) = 0.0393.The iron is pentacoordinate, with a geometry intermediate between trigonal bipyramidal, with a phosphorus and a carbonyl apical, and square pyramidal with a carbonyl apical.No significant differences are observed between the Fe-P distances (av. 2.224(2) Angstroem) or between the Fe-CO distances (av. 1.770(5) Angstroem).Comparison with the analogous bis(diphenylphosphino)methane derivative shows that the main differences in the coordination polyhedra arise from the difference in the P...P bite distance, which is 2.981(2) Angstroem in the ethane derivative but only 2.650(3) Angstroem in the methane derivative.The five-membered Fe-P-C-C-P chelate ring shows an unsymmetrical conformation, with one carbon atom tending to lie in the P-Fe-P plane, the corresponding torsion about the Fe-P bond being almost zero (1.3(2) grad).This kind of conformation is common for bis(diphenylphosphino)ethane chelating rings, suggesting a limited flexibility of that ring.The orientations of the phenyl groups are somewhat different from those in the corresponding bis(diphenylphosphino)methane complex.
REACTION OF η4-DIENE-AND η4-HETERODIENE-IRON CARBONYL COMPLEXES WITH 1,2-BIS(DIPHENYLPHOSPHINO)ETHANE: A ROUTE TO DICARBONYL TRISPHOSPHINE IRON COMPLEXES
Bellachioma, G.,Cardaci, G.
, p. 91 - 98 (2007/10/02)
The reaction of 1,2-bis(diphenylphosphino)ethane with (η4-diene)- and (η4-heterodiene)-Fe(CO)2L complexes gives the complex .A mechanism for the formation of this complex is proposed on the basis of the reaction products and the kinetic results.
Kinetics and Mechanism of Mono- and Di-olefin Exchange at Five-co-ordinate Iron(0)
Burkinshaw, Philip M.,Dixon, Denis T.,Howell, James A. S.
, p. 999 - 1004 (2007/10/02)
Exchange of various mono-olefins with styrene in proceeds via a dissociative process, involving an Fe(CO)4 intermediate.Ligand exchange in system (i) (enone = benzylideneacetone, cinnamaldehyde, chalcone, or dypnone; polyene = cyclohexa- and cyclohepta-1,3-diene, cycloheptatriene, cyclo-octatetraene, 4-enone)> + polyene (*) 4-polyene)> + enone (i) or 1,4-diphenylbuta-1,3-diene) is stepwise, involving a rate-determining dechelation of the ?-bound CO moiety.Both associative and dissociative pathways are found.The influence of diene structure and enone substituent is discussed.
