Iron complexes triphenylphosphine

As already mentioned earlier, the ruthenium complex [Ru(bdmpza) Cl(PPh3)2l (24) easily releases one of the two phosphine ligands and allows the substitution not only of a chlorido but also of a triphenylphosphine ligand for K -coordinating carboxylato or 2-oxocarboxylato ligands (58). The purpose of these studies was to find structural ruthenium models for the active site of 2-OG dependent iron enzymes, since ruthenium(II) complexes are low spin and thus suitable for NMR characterization, whereas ferrous iron complexes with NJV,0-ligands are often difficult to investigate, due to their... 

A chiral metal center, as is found in a pseudotetrahedral iron complex with cyclopentudienyl. carbonyl, triphenylphosphine, and ethyl ligands, hus also beer used to address the question of alkyl migration versus carbonyl insertion. Inversion of... 

Dicarbonyltris(phosphane)iron complexes have been known for more than 30 years. In 1960, Manuel and Stone prepared the complex Fe(CO)2[P(C6H5)3]3 in low yields (4-13%) by the reaction of a (diene)- or (triene)tricarbonyliron complex with an excess of triphenylphosphine in refluxing ethylcyclohexane.1... 

Aceto(carbonyl)cyclopentadienyl(triphenylphosphine)iron, CsHsFefCOKCOCH,)-[P(QHs)3] (1). Orange crystals, m.p. 145°, air stable. The chiral iron complex is prepared as a racemate by reaction of CsH5Fe(CO)2CH3 with P(C6H5)j. ... 

Cycloheptodienyl-iron complexes.3 Cycloheptadienyl-Fe(CO)3 reacts with nucleophiles to give mixtures of products, usually in low yield. However, complexes 1, in which one CO ligand is replaced by triphenylphosphine or triphenyl phosphite, react with most nucleophiles at the dienyl terminus and in high yield. Hydride abstraction followed by reaction with a second nucleophile results in a regio- and stereocontrolled substitution at the opposite terminus and again anti to the metal. Decomplexation affords cw-5,7-disub-stituted cycloheptadienes. 

An iron tetracarbonyl complex (295) ° and a platinum bis(triphenylphosphine) complex of thiete 1,1-dioxide have been prepared. Platinum complexes of 3-phenyl- and 3-(p-bromophenyl) thiete 1,1-dioxide also have been prepared. No complex was obtained with the 3-t-butyl derivative. The pale-yellow, crystalline iron complex decomposes in refluxing hexane in the presence of excess sulfone to Fe2S2(CO)9, indicating a drastic structural rearrangement. Other carbon-containing fragments were not observed. The bis(triphenylarsine)platinum complex of 3-02-bromophenyl) thiete sulfone is decomposed photochemically to the thiete sulfone. The same result is achieved on treatment of the complex with tetra-cyanoethylene. ... 

Bis(phosphine) derivatives of pentacarbonyliron are starting materials for the synthesis of several organometallic iron complexes. " Iron carbonyl phosphine complexes have attracted attention because of their relevance to photochemical catalysis of olefin hydrosilation. Though Fe(CO)3(PR3)2 complexes are used widely in organotransition metal chemistry, an efficient preparation of these compounds has not been reported. Clifford and Mukherjee describe two methods for the synthesis of tricarbonyl-bis(triphenyphosphine)iron(0). They report that direct reaction between Fe3(CO)j2 and triphenylphosphine in THF solvent gives a mixture of Fe(CO)3[P(C6Hs)3]2 (27%) and Fe(CO)4[P(C5H5)3] (34%). The second... 

OC, Carbon monoxide (Continued) cobalt, iron, osmium, and ruthenium complexes, 21 58-65 iron complex, 21 66, 68 manganese complexes, 23 34 molybdenum complexes, 23 4-9 niobium complexes, 23 34 palladium complex, 21 49 rhodium complexes, 23 124 ruthenium complex, 21 30 OCH4, Methanol, iridium complexes, 23 127 rhodium complexes, 23 127, 129 OCjHs, Acetone, compd. with carbonyltri-p.-chloro-chlorotctrakis-(triphenylphosphine)diruthcnium (1 2), 21 30... 

MW-mediated synthesis of [(77-arene)(CO)3Mn][PF6] salts was also reported, and a bis-complexed triphenylphosphine iron sandwich complex was obtained from the AlCk-catalyzed ligand-exchange reaction between... 

PBF4O2WC2sH20> Tungsten, dicarbonyl(if -cyclopentadienyl) [tetrafluoroborato-(1 -)] (triphenylphosphine)-, 26 98 PBrF4N3RuCi4H2i, Ruthenium(II), tris-(acetonitrile)bromo(ft -1, S-cyclooctadiene)-, hexafluoro-phosphate(l —), 26 72 PC3H9, Phosphine, methyl-, iron complex, 28 177... 

With the failure of the diisopropylamino group to favour formation of alkylidyne iron complexes we next turned our attention to the possibility of using steric factors to favour alkylidyne formation. The reaction of [Fe(CO)5] with simple aryl or alkyl lithium reagents (LiR R = Me, tBu, C6H4Me-4, C6H40Me-4) followed by trifluoroacetic anhydride and triphenylphosphine lead in all cases to the exclusive formation of [Fe(CO)3(PPh3)2] in high yield (Scheme 9). 

The oxidation of triphenylphosphine has also been investigated using iron complexes as catalysts [133]. Kinetics of this reaction were studied using [Fe(mnt)2] and [Fe(nmt)3] where mnt " is CM-l,2-dicyanoethylene-l,2-dithiolate. Approximately 1 mol of the iron(IV) complex catalyzed the oxidation of 15 mol of triphenylphosphine compared to about 10 mol of triphenylphosphine for the iron(III) complex. The rate of oxygen uptake in the presence of either complex was found to be proportional to the concentrations of both triphenylphosphine and the iron complex but independent of oxygen pressure. No evidence was obtained for the formation of molecular oxygen complexes. 

Pyridazines form complexes with iodine, iodine monochloride, bromine, nickel(II) ethyl xanthate, iron carbonyls, iron carbonyl and triphenylphosphine, boron trihalides, silver salts, mercury(I) salts, iridium and ruthenium salts, chromium carbonyl and transition metals, and pentammine complexes of osmium(II) and osmium(III) (79ACS(A)125). Pyridazine N- oxide and its methyl and phenyl substituted derivatives form copper complexes (78TL1979). 

---