16923-76-5Relevant articles and documents
Synthesis of iron arylphosphonate complexes
Gibson, Dorothy H.,Ong, Tek-Sing,Ye, Ming,Franco, Jaime O.,Owens, Kathryn
, p. 2569 - 2570 (1988)
Reactions of cationic iron complexes bearing aryl phosphite ligands, (η-C5H5)Fe(CO)2(L)+BF 4- [L = P-(OPh)3 or P(O-p-tolyl)3] and (η-C5Me5)Fe(CO)2 [P(OPh)3]+-BF4-, with aqueous base give the corresponding phosphonate complexes quickly and in good yields. Alternatively, (η-C5H5)Mo(CO)3[P(OEt)3] +BF4- and trans-Mn-(CO)4[P(OPh)3]2+BF 4- give hydrides under the same reaction conditions. A pathway involving intramolecular oxygen transfer from intermediate metallocarboxylate anions is suggested to account for the results with the iron compounds.
Preparation of new 'diazo' complexes of manganese stabilised by phosphite ligands
Albertin, Gabriele,Antoniutti, Stefano,Bordignon, Emilio,Perinello, Giampaolo
, p. 217 - 230 (2007/10/03)
A series of mono- and binuclear aryldiazene complexes [Mn(ArN=NH)(CO)nP5-n]BPh4 and [{Mn(CO)nP5-n}2(μ-HN=NAr-ArN=NH)](BPh4)2 [P=P(OMe)3, P(OEt)3 or P(OPh)3; Ar=C6H5, 4-CH3C6H4; Ar-Ar=4,4′-C6H4-C6H4, 4,4′-C6H4-CH2-C6H4; n=1, 2 or 3] were prepared by allowing hydride species MnH(CO)nP5-n to react with the appropriate aryldiazonium salts at -80°C. Characterisation of the complexes by IR and variable-temperature 1H-, 31P-, 15N-NMR spectra (with 15N isotopic substitution) are reported. Treatment of aryldiazene derivatives containing both the tricarbonyl Mn(CO)3P2 and the dicarbonyl Mn(CO)2P3 fragments with NEt3 affords the pentacoordinate dicarbonyl aryldiazenido Mn(ArN2)(CO)2P2 and [Mn(CO)2P2]2(μ-N2Ar-ArN2) derivatives. Instead, the aryldiazene bonded to the monocarbonyl fragment Mn(CO)P4 is unreactive towards base and does not give aryldiazenido species. Hydrazine complexes [Mn(RNHNH2)(CO)nP5-n]BPh4 [R=H, CH3 or C6H5; P=P(OMe)3, P(OEt)3 or P(OPh)3; n=1, 2 or 3] were prepared by reacting hydride species MnH(CO)nP5-n first with Br?nsted acid (HBF4 or CF3SO3H) and then with an excess of the appropriate hydrazine. The binuclear complex [{Mn(CO)3[P(OEt)3]2}2(μ-NH2NH2)](BPh4)2 was also prepared. Oxidation reactions of phenylhydrazine cations [Mn(C6H5NHNH2)(CO)nP5-n]+ with Pb(OAc)4 at -40°C give the phenyldiazene [Mn(C6H5N=NH)(CO)nP5-n]+ derivatives, whereas the oxidation of methylhydrazine [Mn(CH3NHNH2)(CO)nP5-n]+ complexes allows the synthesis of the first methyldiazene [Mn(CH3N=NH)(CO){P(OMe)3}4]BPh4 derivative of manganese.
Synthesis and thermolysis of neutral metal formyl complexes of molybdenum, tungsten, manganese, and rhenium
Gibson,Owens,Mandal,Sattich,Franco
, p. 498 - 505 (2008/10/08)
The possible intermediacy of catalyst-bound formyls in syngas transformations has prompted efforts to prepare and study the chemistry of transition-metal formyl complexes over more than a decade. We have used a mild borohydride in our reactions with metal carbonyl cations and have introduced some variations into the syntheses which allow, in almost all cases, for the pure formyl complex to be precipitated from solution as it is formed. The formyl complexes and their cationic precursors are shown. Seven of the formyls are new; improved procedures have been established for the other four. All but one of the compounds have been isolated.
ELECTROOXIDATION OF METAL CARBONYL ANIONS. FORMATION AND REACTIVITY OF 17-ELECTRON MANGANESE(0) RADICALS
Kuchynka, D. J.,Amatore, C.,Kochi, J. K.
, p. 133 - 154 (2007/10/02)
The series of carbonylmanganese anions Mn(CO)3P2-, with P = phosphites and phosphines, undergo reversible anodic oxidation to the 17-electron radicals Mn(CO)3P2. in tetrahydrofuran solutions.The reactivity of the carbonyl-manganese radicals of Mn(CO)3P2. is evaluated in the context of hydrogen atom transfer from tributyltin hydride.The donor properties of the carbonylmanganates are strongly modulated by the ligands - the reversible oxidation potentials E1/2 of phosphine-substituted anions being significantly more negative than those of the phosphite analogs.By contrast the reactivity of the phosphine- and phosphite-substituted radicals are not differentiated by electronic factors.However steric effects (as indicated by the cone angle of the phosphite or phosphine ligand play a strong role in determining the reactivity of these 17-electron radicals.The combination of cyclic voltammetry, chronoamperometry, coulometry, and product analysis is used to establish the mechanism of hydrogen transfer from tribultyn hydride to Mn(CO)3P2. in THF solutions.The measurement of the second-order rate constants k2 for hydrogen transfer by double potential step chronoamperometry (DPSC) is described.
Synthesis of Cationic Mer-Phosphite-Substituted Carbonylmanganese Compounds
Berke, Heinz,Weiler, Gertrud
, p. 431 - 437 (2007/10/02)
Di-, tri- and tetrasubstituted carbonylmanganese compounds (OC)nL6-nMn(+)PF6(-) (L = P(OMe)3, P(OEt)3, P(O-i-Pr)3, P(OPh)3 and P(O-o-Tolyl)3) are synthesized by hydride abstraction and substitution processes from corresponding hydridemanganese compounds. - Key words: Phosphite Substitution, Carbonylmanganese Cations, Hydride Abstraction
HYDROGEN ABSTRACTION AND DIMERISATION REACTIONS OF SOME ORGANO-TRANSITION METAL FREE RADICALS
Armstead, Judith A.,Cox, David J.,Davis, Reg
, p. 213 - 220 (2007/10/02)
The 17-electron species (M=Mn, Re, x=0; M=Mn, Re; L=Ph3P, x=1, 2; M=Mn, Re; L=(o-MeC6H4O)3P, x=2; M=Mn; L=(p-ClC6H4O)3P, (PhO)3P, x=2; M=Mn; L=P(OMe)3, x=3) have been generated by one electron oxidation of the corresponding anions and show ty
