68643-82-3Relevant academic research and scientific papers
Fe(CO)22L, Dicarbonylbis(trimethylphosphit)eisen-Komplexe mit den Liganden L = Ethen, Diphenylethin und SO2
Meier-Brocks, Frank,Albrecht, Reinhard,Weiss, Erwin
, p. 65 - 77 (1992)
The ethene ligand in Fe(CO)22(η2-C2H4) (1) can be substituted by reaction of 1 with diphenylethine leading to formation of the previously known Fe(CO)22(η2-C2Ph2) (3).This reaction represents a new path to the hitherto rare mononuclear η2-alkine iron complexes.Another related compound, Fe(CO)22(SO2) (4) was found unexpectedly upon reacting 1 with thiophenedioxide, and was prepared subsequently from 1 and SO2. Compounds 1, 3 and 4 have been characterized by crystal structure analyses.Their structures are very similar, having trigonal-bipyramidal coordination of the iron atom and phosphite groups in trans positions.They only differ by the ligands ethene, diphenylethine or SO2 in equatorial positions.
Enhanced substitutional lability of [Fe(CO)2{P(OPh)3}2(η2- PhCCPh)]: Facile insertion of CO and organoisocyanides into iron-alkyne bonds
Barrow,Cromhout,Manning,Gallagher
, p. 1352 - 1358 (2007/10/03)
The η2-alkyne complex [Fe(CO)2{P(OPh)3}2(η2- PhCCPh)] 1 reacts readily with PR3 to give [Fe(CO)2{P(OPh)3}-(PR3)(η2- PhCCPh)], and then [Fe(CO)2(PR3)2(η2-PhCCPh)] (R = OMe, 2a; OEt, 2b; OnBu, 2c; Me, 2d; nBu, 2e; Ph, 2f). The ability of the alkyne ligand to act as a four-electron donor to a ligand-dissociated 16-electron reaction intermediate promotes site-specific replacement of the axial phosphite ligands; there is no evidence for equatorial CO replacement. Reaction of 1 with CO affords six-coordinate ferracyclopent-3-ene-2,5-dione (maleoyl) complexes [Fe(CO)m{P(OPh)3}n {η1:η1-C(O)C(Ph)C(Ph)C(O)}] (m = 3, n = 1, 3; m = n = 2, 4a) in which CO groups have inserted into each of the Fe-C(alkyne) bonds. Analogues of 4a, [Fe(CO)2{P(OR)3}2 {η1:η1-C(O)C(Ph)C(Ph)C(O)}] (R = Me, 4b; Et, 4c), are similarly obtained as the sole products from the reaction of CO with 2a and 2b, respectively. The mechanism proposed for this reaction depends on replacement of an axial phosphite ligand by CO which is then susceptible to migratory attack by C(alkyne), whereas the existing equatorial CO ligands are not. The crystal structure of 3 has been determined: the complex exhibits a distorted octahedral geometry about the iron centre with a facial arrangement of the three CO ligands and the remaining coordination sites occupied by the P(OPh)3 ligand and by the two C(O) groups of the maleoyl moiety. Reaction of 1 and CNR (R = Me and Ph) also proceeds via alkyne-CNR coupling to give [Fe(CO)2{P(OPh)3} {η1:η1:η1:η1- C(=NR)=C(Ph)C(Ph)=C(=NR)}] which is proposed to have a square pyramidal geometry on the basis of spectroscopic data.
Koordination und Chemie von Acetylenen an Dicarbonylbis(trimethylphosphit)eisen-Fragmenten
Birk, Reiner,Groessmann, Ulrich,Hund, Hans-Ulrich,Berke, Heinz
, p. 321 - 330 (2007/10/02)
The μ-dinitrogenbis complex (1) reacts with acetylenes R1CCR2 (R1, R2 = H, Ph) to yield the acetylene substitution products, (OC)22Fe(R1CCR2) (R1, R2 = Ph, 2a; R1 = H, R2 = Ph, 2b; R1 = R2 = H, 2c) under elimination of N2. 2b and 2c undergo reversible insertion into the acetylenic C-H bond to yield the acetylide hydrido species (R2 = Ph, 3b; R2 = H, 3c).The reaction of 1 with methyl propiolate leads to a carbonyl-2,4,6-tris(methoxycarbonyl)hexa-1,3,5-triene-1,5-diyl-bis(trimethylphosphite)iron compound (5), which has been characterized by an X-ray diffraction study.
