40757-44-6

Upstream product

• 17685-52-8 triiron dodecarbonyl 
• 1486-28-8 diphenyl(methyl)phosphine 
• 38720-22-8 (2-methyl-4-phenyl-1-oxabuta-1,3-diene)tricarbonyliron⁽⁰⁾ 
• 16940-66-2 sodium tetrahydroborate 
• 13463-40-6 iron pentacarbonyl 
• 37410-36-9 Fe(CO)4PPh₂Me 
• 18475-02-0 Fe(CO)4(PMe₃) 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 15616-56-5 diiodotetracarbonyliron(II) 

Downstream Products

• 136706-68-8 {Fe(H)(CO)3(PCH₃(C₆H₅)2)2}⁽¹⁺⁾*CF₃SO₃^(1-)={Fe(H)(CO)3(PCH₃(C₆H₅)2)2}CF₃SO₃ 

Relevant academic research and scientific papers

Reductive elimination of halogens assisted by phosphine ligands in Fe(CO)4X2 (X = I, Br) complexes

Fe(CO)4X2 complexes [X = I (1), Br(1′)] react with phosphine ligands L (L = PMe3, PEt3, PMe2Ph, PMePh2, PPh3) via a two-step mechanism: in the first step fac-Fe(CO)3LX2 complexes are formed; in the second step two parallel pathways, a and b, are observed; in pathway a, reductive elimination with formation of equimolar amounts of Fe(CO)3L2 (5) and phosphonium salts [LX]+X- is observed; in pathway b, disubstituted dihalide complexes cis,trans,cis-Fe(CO)2L2X2 are formed. The relative weights of pathways a and b depend on the basicity, steric hindrance and concentration of ligand L, on the nature of the halogen and on temperature. A radical mechanism which accounts for most of the experimental results is proposed.

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

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.

Use of BF4 to prepare thiolate complexes of iron and ruthenium

The complexes BF4 (L = PPh2Me, PPhMe2 P(OMe)3), 3SMe>BF4, and BF4 were prepared by reactions of BF4 and the appropriate neutral M(CO)5-n(L)n precursor.Several other analogous reactions were unsu

Heats of protonation of transition-metal complexes: The effect of phosphine basicity on metal basicity in CpIr(CO)(PR3) and Fe(CO)3(PR3)2

Titration calorimetry has been used to determine the effects of phosphine ligand basicity on the heats of protonation (ΔHHM) of the metal in the CpIr(CO)(PR3) and Fe(CO)3(PR3)2complexes (PR3/sub

Preparation and characterization by 31P-NMR spectroscopy of mixed disubstituted complexes

The disubstituted complexes , where L and L' are different phosphine ligands have been prepared by reaction of the hydrosilyl derivatives with L'.Good results were obtained for L = PMe3 and L' = PPh3, P(OPh)3, P(OEt)3 or P(O-i-Pr)3 but with L' = PMe2Ph, PMePh2, PEt3, a mixture of homo and mixed disubstituted derivatives were obtained.The results can be interpreted in terms of exchange of the L ligand in 3 with L'.The variations in the 31P NMR chemical shifts and 2JPP coupling constants are discussed in the light of the properties of the ligands, and good correlations are revealed with the cone angle and the pKa, respectively.

A Facile, high-yield synthesis of trans-Fe(CO)3(PR3)2 from Fe(CO)5, Fe(CO)4CHO-, HFe(CO)4-, or HFe(CO)3PR3-

The reaction of Fe(CO)5 with PR3 and NaBH4 in refluxing n-butyl alcohol affords high yields of trans-Fe(CO)3(PR3)2. It has been shown that Fe(CO)4PR3, which does not appear in the collected product, is also not a significant intermediate in the reaction. The reaction proceeds by initial formation of H2 gas and Fe(CO)4CHO-. The formyl complex decomposes to HFe(CO)4- which reacts with PR3 to give the disubstituted product. The principal intermediate for this substitution is believed to be HFe(CO)3PR3-, although polynuclear species may also be important. The substitution of HFe(CO)4- by PR3 is favorable when the counterion is Na+ but not when it is PPN+. The overall reaction is very sensitive to choice of solvent; substitution of ethanol for n-butyl alcohol leads to greatly reduced yields.

PHOTOLYTIC PREPARATION OF (BENZYLIDENEACETONE)CARBONYLPHOSPHINEIRON(0) COMPLEXES. THE MOLECULAR STRUCTURES OF Fe(CO)2(PEt3)(bda) AND Fe(CO)2(PPhMe2)(bda) (bda = benzylideneacetone)

The (benzylideneacetone) carbonylphosphine iron(0) complexes, Fe(CO)2L(bda), Fe(CO)L2'(bda) and Fe(CO)(dpe)(bda) (L = PEt3, PPhMe2, PPh2Me; L' = PPhMe2, PPh2Me; dpe = 2) have been prepared by irradiating the corresponding tetracarbonylmonophosphine iron(0), tricarbonyldiphosphine iron(0) or tricarbonyl-1,2-bis(diphenylphosphine)ethane iron(0) complexes in benzene in the presence of benzylideneacetone.The X-ray crystal structures of the complexes with L = PEt3 (A) and PPhMe2 (B) have been determined, and show that the Fe atom adopts a distorted octahedral coordinated geometry in which three of the sites are occupied by the bda ligand.The bond parameters in the bda ligand suggest that this coordinated group is intermediate between its ground and first excited states.The complex Fe(CO)2(PEt3)(bda) crystallises in the monoclinic space group P21/c with a 10.203(3), b 12.964(4), c 16.960(6) Angstroem, β 120.00(2) deg, and Z = 4.The structure was solved by a combination of Patterson and Fourier difference techniques and refined by blocked full matrix least squares to R = 0.035 for 3351 unique observed diffractometer data.The complex Fe(CO)2(PPhMe2)(bda) also crystallises in space group P21/c, with a 8.134(3), b 21.394(8), c 11.658(5) Angstroem, β 108.12(2) deg and Z = 4.The structure was solved and refined as above to R = 0.036 for 3498 diffractometer data.The IR and 1H NMR data for all the complexes studied agree with the observed structures.

THE TRANSITION METAL CATALYZED REACTION BETWEEN Fe(CO)5 AND GROUP V DONOR LIGANDS. A FACILE, HIGH YIELD SYNTHESIS OF Fe(CO)4PPh3

The reaction of Fe(CO)5 and L (L=Group V donor ligand), in the presence of CoCl2 * 2 H2O or CoI2 * 4 H2O as catalyst, results in the synthesis of Fe(CO)4L in good yield.Unusual reactivity patterns for the substitution of CO on Fe(CO)5 by L have been found; for CoI2 as catalyst the reaction rate increases in the order PPh3 ca.AsPh3 ca.P(OPh)3 > SbPh3 > PPh2Me > PPhMe2 > P(C6H11)3 > P(OEt)3 > P(n-Bu)3 > P(OMe)3.These results are interpreted in terms of the variation of the catalyst through interaction of CoX2 with L.