1025-36-1Relevant academic research and scientific papers
Preparation, characterization, and reactions of 16-electron Ta(η5-C5Me5)(η3-1-phenylallyl)2
Mashima, Kazushi,Yamanaka, Yoshimichi,Gohro, Yoshihiko,Nakamura, Akira
, p. 131 - 138 (1993)
Treatment of Cp*TaCl4 with 4 equiv of phenylallylMgBr in THF afforded Cp*Ta(1-phenylallyl)2 (2), whose structure was characterized by a single crystal X-ray study as 16-electron two legged piano stool with two allyl moieties in supine-supine geometry.In this reaction, the starting TaV complex was reduced to a TaIII species accompanying the formation of reductive allyl-coupling products, diphenyl-1,5-hexadiene derivatives 3. ?-Donor molecules such as carbon monoxide, tert-butyl isocyanide, isocyanates and isothiocyanates induced the coupling reaction of two phenylallyl groups on tantalum to give 1,6-diphenyl-1,5-hexadiene (3a).The intermediate Cp*Ta(tert-BuNC)2(η2,η2-1,6-diphenyl-1,5-hexadiene) (5) was characterized by 1H NMR spectroscopy.Complex 2 was the catalyst precursor for the selective dimerization of isocyanates.Oxygen donor molecules such as DMSO and pyridine-N-oxide reacted with 2 to afford 1:1 adducts.One-electron oxidation of 2 with ferrocenium cation resulted in the formation of 1-phenyl-1-propene.The TaIV complexes, *Ta(1-phenylallyl)2>, were obtained by the reaction of 2 with TCNQ and DDQ.
Investigation into the reactivity of oxoniobocene complexes [Cp*2Nb(=O)R] (Cp=η5-C5Me5; R=H, OH, OMe) towards heterocumulenes: Formation of carbamato and thiocarbamato complexes and catalytic cyclization of PhNC
Blacque, Olivier,Brunner, Henri,Kubicki, Marek M.,Leblanc, Jean-Claude,Meier, Walter,Moise, Claude,Mugnier, Yves,Sadorge, André,Wachter, Joachim,Zabel, Manfred
, p. 47 - 54 (2007/10/03)
The reaction of [Cp*2NbCl2] (Cp=η5-C5Me5) with KOH or Ba(OH)2·8H2O in THF was investigated under slightly modified conditions. In addition to the known complex [Cp*2Nb
Tris(trimethylphosphine)cobalt(0) Compounds Containing Azaolefinic Ligands - Syntheses and Structures of Benzocinnoline and Phenylisocyanate Complexes
Klein, Hans-Friedrich,Helwig, Michael,Karnop, Michael,Koenig, Herbert,Hammerschmitt, Birgit,et al.
, p. 785 - 793 (2007/10/02)
Mononuclear cobalt(0) complexes Co(η2-azaolefin)(PMe3)3 (azaolefin = benzocinnoline (1), p-dimethylamino-phenyl(phenyl)diazene (2), 1/2 diazobenzene (3), bis(p-tolyl)diazene (4), bis(p-fluorophenyl)diazene (5), bis(p-trifluoromethyl-phenyl)diazene (6), phenylisocyanate (7)) are obtained from Co(cyclo-C5H8)(PMe3)3 by substitution of the olefin.X-ray crystal structure determinations of 1 and 7 show tetrahedral arrangements of ligands around the cobalt atom.By reaction with carbon monoxide carbonyl(phosphine)cobalt(0) complexes are formed. 7 catalyses the cyclotrimerization of phenylisocyanate, while with CoCl(PMe3)3 as a catalyst the cyclic dimer of phenylisocyanate is selectively formed.A convenient synthesis for CoCl(PMe3)3 is described. Key words: Azobenzene, phenylisocyanate; cobalt(0) complexes, synthesis, structure.
SYNTHESIS AND CERTAIN REACTIONS OF HETEROCYCLIC AMIDES OF 1,3,4,2-OXADIAZAPHOSPHOLINE
Yusupov, M. M.,Razhabov, A.
, p. 979 - 983 (2007/10/02)
Heterocyclic 1,3,4,2-oxadiazaphospholine amides were synthesized and the influence of the amide residue on the reactivity of these compounds in reactions with sulfur, phenyl isocyanate, carbonyl compounds and Schiff bases was disclosed.
Further studies of cluster-bound imido ligands. Imido-acyl coupling and promotion of the formation and carbonylation of imido ligands by halides
Han, Sung-Hwan,Song, Jeong-Sup,Macklin, Phillip D.,Nguyen, Sonbinh T.,Geoffroy, Gregory L.,Rheingold, Arnold L.
, p. 2127 - 2138 (2008/10/08)
Halides, cyanide, and hydride ligands have been shown to promote the formation of imido ligands from nitrosobenzene as evidenced by the rapid reaction which occurs to form the cluster anions [Ru3(μ3-NPh)(X)(CO)9]- (X = Cl, Br, I, CN, H) when nitrosobenzene is added to solutions of [Ru3(X)(CO)n]- (n = 10, 11). The halide and cyanide derivatives also result from addition of the appropriate [(Ph3P)2N]X salt to the imido cluster Ru3(μ3-NPh)(CO)10. The salt [Na(18-crown-6)][Ru3(μ3-NPh)(I)(CO)9] has been structurally characterized: P1, a = 10.369 (3), b = 13.335 (3), c = 13.738 (3) A?, α = 79.54 (2), β = 77.03 (2), γ = 86.76 (2)° V = 1820.1 (6) A?3, Z = 2, R(F) = 4.55%, R(wF) = 5.20% for 5663 reflections (4σ(Fo)). Its structure is similar to that of the parent cluster Ru3(μ3-NPh)(CO)9(μ3-CO), with the iodide having replaced a CO in a position trans to the μ3-CO ligand. The anion promotion of the nitrosobenzene deoxygenation reaction is believed to result from the anions promoting loss of CO and formation of an intermediate with a coordinated nitrosobenzene which quickly deoxygenates to form CO2 and the imido ligand. Support for this suggestion comes from the observation that the cluster Ru3(μ3-NPh)(CO)10 rapidly forms in high yield upon addition of PhNO to Ru3(CO)11(CH3CN). Similar reactions of PhNO and ButNO with acetonitrile-substituted clusters have been used to prepare Os3(μ3-NPh)(CO)10, the new heteronuclear clusters Fe2Ru(μ3-NPh)(CO)10 and FeRu2(μ3-NPh)(CO)10, and the mixed-substituent bis(imido) cluster Ru3(μ3-NPh)(μ3-NBut)(CO) 9. The heteronuclear cluster anion [CoRu2(μ3-NPh)(CO)9]- has also been prepared by a metal-exchange reaction via addition of [Co(CO)4]- to Ru3(μ3-NPh)(CO)10. Protonation of this anion gives the hydride cluster HCoRu2(μ3-NPh)(CO)9 which has been structurally characterized: P1, a = 8.609 (2), b = 15.547 (4), c = 15.721 (4) A?, α = 85.07 (2), β = 75.97 (2), γ = 79.58 (2)° V = 2005.8 (9) A?3, Z = 4, R(F) = 4.17%, R(wF) = 5.26% for 5172 reflections (3σ(Fo)). The cluster consists of a CoRu2 triangle with a triply bridging imido ligand and with the hydride bridging the two Ru atoms. Halides have also been found to promote the carbonylation of imido ligands to form isocyanates as illustrated by the rapid reactions which occur to form PhN=C=O when the cluster anions [Ru3(μ3-NPh)(X)(CO)9]- (X = Cl, Br, I) are placed under 1 atm of CO at 22°C. In contrast, the cluster anions [Ru3(μ3-NPh)(X)(CO)9]- (X = CN, H) do not react with CO under these mild conditions, although the anion [CoRu2(μ3-NPh)(CO)9]-readily carbonylates to form Ru3(CO)12, [Co(CO)4]-, and [PhNCO]2 under slightly more forcing conditions. Acyl-substituted clusters [Ru3(μ3-NPh)(CO)9(C{O}R)]- (R = Me, Ph) form upon reacting Ru3(μ3-NPh)(CO)10 with the appropriate RLi reagent, and the acyl ligands in these clusters migrate to the imido ligands when placed under CO. The resultant amido clusters have been protonated to form the hydride species HRu3{μ2-N(Ph)C(O)R}(CO)10 which undergo reductive elimination of the amide PhNHC{O}R when placed under a CO atmosphere. The possible relevance of these various imido transformations to nitroaromatic carbonylation catalysis is discussed.
