49655-12-1Relevant academic research and scientific papers
Alkylation and substitution reactions of metal carbonyl acylate and carbene complexes
Conder,Darensbourg, M. York
, p. 506 - 511 (1974)
Alkylation reactions of trans-LFe(CO)3C(O)R-Li+, where L = CO, PPh3, P(n-Bu)3, P(OMe)3, and P(OPh)3 and R = Ph, Me, and benzyl, employing as alkylating agents MeI, MeOSO2/s
Phosphorus-phosphorus coupling constants in mixed-phosphine tricarbonyl iron complexes, Fe(CO)3LL′. Crystal structure of trans-Fe(CO)3(PEt3) (PPh3)
Keiter, Richard L.,Benson, John William,Keiter, Ellen A.,Harris, Travis A.,Hayner, Matthew W.,Mosimann, Laura L.,Karch, Eric E.,Boecker, Carol A.,Olson, Donna M.,Vanderveen, Jennaver,Brandt, Douglas E.,Rheingold, Arnold L.,Yap, Glenn P.A.
, p. 2246 - 2253 (2008/10/08)
Mixed-ligand complexes, trans-Fe(CO)3LL' (L = PPh2Me, L' = PPh2Me, PPhMe2, PMe3, PPh2-Et, PEt3, PPh2CH=CH2, PPh2H, AsPh3, P(OPh)3; L = PMe3, L' = PEt3, PPh2Et, PCy3, PPh2Me, PPhMe; L = PEt3, L' = PPh2Me; L = PPh2H, L' = PPh2CH=CH2, PPh2Et; L = AsPh3, L' = PPhMe2, P(OPh)3, P(OMe)3, P(OEt)3), have been obtained from the stepwise reaction of phosphines with Fe(CO)3(BDA) (BDA = benzylideneacetone) or Fe(CO)3(AsPh3)2 and from the reaction of phosphine with Fe(CO)4PPh3 in the presence of base. A strong negative correlation exists between 2Jpp coupling constant values and the sum of the phosphine pKa values. By application of quantitative analysis of ligand effects, it has been shown that 2Jpp for the mixed-ligand complexes correlates strongly with both γ and Ear, but not with θ. Although a near perfect fit is obtained from the three-parameter equation, a statistical analysis suggests that for this small data set there are no predictive advantages over the one-parameter pKa model. It is possible to calculate reliable 2Jpp values for transFe(CO)3L2 complexes with either model. An X-ray structure of solid-state frans-Fe(CO)3-(PEt3)(PPh3) shows equal Fe-PEt3 and Fe-PPh3 bond distances, implying that bond strength equalization may occur when two rather different phosphines occupy trans coordination sites.
Preparation and Spectroscopic Characterization of trans-Fe(CO)3L1L2 (L1, L2 = Phosphine or Phosphite)
Inoue, Hidenari,Kuroiwa, Takeshi,Shirai, Tsuneo,Fluck, Ekkehard
, p. 641 - 646 (2007/10/02)
The 57Fe Moessbauer spectra of mixed ligand complexes of the type trans-Fe(CO)3L1L2 (L1 = triphenylphosphine or triphenylphosphite and L2 = phosphine or phosphite) show a quadrupolesplitting doublet typical of the disubstituted iron carbonyls in trigonal bipyramidal symmetry.The inverse linear dependence of the isomer shifts on the CO stretching frequencies is interpreted on the basis of the strengthening triple-bond nature of the carbonyl ligands with increasing iron-to-phosphorus ?-back donation.A linear correlation, with a positive slope, between the isomer shifts and the quadrupole splittings has revealed that the phosphorus-to-iron ?-donation is offset by the iron-to-phosphorus ?-back donation.A corrlation between the coordination shifts and the isomer shifts demonstrates that the iron-to-phosphorus ?-back donation plays an important role in the Fe-P bond.The relatively large coupling constant of 2J(P,P) reflects a strong interaction between trans-phosphorus ligands through the P-Fe-P bond. - keywords: (Phosphine/Phosphite)tricarbonyliron, Moessbauer Spectra, IR Spectra, 31P NMR Spectra
