Triphenylphosphine complexes with iron

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). 

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... 

Wilkinson (9) isolated the tetrakis(trihalogenophosphine)nickel compounds Ni(PX3)4 (X= F, Cl, Br), and Behrens (10) isolated the triphenylphosphine complex Ni[P(C6H5)3]4 via [Ni(CN)4]4. With iron pentacarbonyl, isonitriles and phosphines yield (11) mono- and disubstituted derivatives, Fe(CO)4L and Fe(CO)3L2, respectively, the latter being the well-known cyclization catalyst of Reppe (7). With the same ligands, carbonyls of the chromium group afforded pentacarbonyl derivatives M(CO)5L. However,... 

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-3,4-(trifluoromethyl)-l,2-diselenete 651 is prepared by refluxing selenium with hexafluoro-2-butyne. It reacts with triphenylphosphine and triphenyl-arsine. Triphenylphosphine selenide was isolated, but no other compounds were identified.Ring-opened complexes with nickel, copper, vanadium, molybdenum (652), tungsten, iron, and cobalt are analogous to complexes of the 1,2-dithiete (527) (Section XXXV.2.C.). 

Pyridazine forms a stable adduct with iodine, with semiconductor properties. " Similar complexes were prepared from iodine mono-ehloride, bromine, and nickel(II) ethyl xanthate. Complexes of pyrida-zines with iron carbonyls and with iron carbonyls and triphenylphosphine have been prepared and investigated. " Complexes of pyridazines with boron trihalides, silver salts, mercury(I) salts, iridium salts, " ruthenium salts, and chromium carbonyls are re-... 

The simplest compounds of this type are the tetraalkylaurates(lll), prepared by the reaction of trialkyl(triphenylphosphine)gold(III) complexes with alkylUthiums, which proceeds by phosphine displacement as illustrated in equation 84. Recent studies have shown the reaction to be stereoselective, with cis- (or tram-) dimethylaUcylgold(lll) complexes giving square planar cis- (or Irons-) tetraalkylaurates and an associative mechanism involving a pentacoordinate gold(III) intermediate has been postulated . ... 

Diphenylcyclopropenone reacted with 2equiv. MejSiCN in the presence of complexes of iron, nickel, rhodium, platinum, and iridium to give 5-amono-2-furancarbonitrile 149 in 41-62% yields (Scheme 2.112) [170]. The triphenylphosphine catalyst exhibited superior activity toward the reaction (55% yield at 60 °C). 

The reactions of various iron carbonyl complexes, such as Fe(GO)4(NMe3), with allene compounds under photo-lytic conditions, yield chelated 77 -allyliron complexes. Two brief reviews discussing the chemistry and application to organic synthesis of these (7r-allyl)tricarbonyl iron lactone complexes have appeared recently. Reaction of the iron lactone complexes with trimethyloxonium tetrafluoroborate yields the carbene complex 23 in good yields. Treatment of the cationic carbene complex with triphenylphosphine results in substitution at the terminal end of the allyl ligand of the trimethylenemethane complex 24. 

Epoxy alcohols are the normal products of the [VO(acac)2]+(Me2C(CN)N a -catalysed oxidation of cyclic olefins by dioxygen however, cyclo-octene is oxidized exclusively to cyclo-octene oxide. The oxidation of sulphides and alkenes by peroxides with a [V(0)(acac)2] catalyst have been compared and the nature of the monoperoxovanadium(v) intermediate investigated. Complexation of a Cr(CO)3 unit to aromatic hydrocarbons enhances the benzylic positions towards attack by superoxide ion, e.g., diphenylmethane is readily converted into benzophenone. Metal porphyrin complexes ML4 continue to attract attention both as reversible oxygen-carriers (M = Fe) and oxidation catalysts (M = Mn, Fe, or Co ). For example [Mn (=0 IPh)(TPP)Cl] is believed to be involved in the oxidation of cyclohexene to cyclohexanol by PhIO in the presence of [Mn(TPP)]+ and a ferryl intermediate [Fe (0)L4] has been proposed in the oxygenation of triphenylphosphine with iron(ii) porphyrin. [M(TPP)]X (M=Mn, X = OAc M=Fe, X=C1 M = Co, X=Br) catalyses the epoxidation of styrene and cyclohexene with NaOCl under phase-transfer conditions. ... 

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