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1.
The addition of reactive carbanions to tricarbonyl(η4-1,3-diene)iron(0) complexes proceeded at ?78 °C to give putative tricarbonyl(η1,η2-but-3-en-1-y1)iron(0) anion complexes and at 25 °C to produce postulated tricarbonyl(η3-allyl)iron(O) anion complexes; trapping of reactive intermediates with dioxygen produced γ,δ-unsaturated acids and allylic alcohols, respectively. 相似文献
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The addition of reactive carbanions to tricarbonyl(η4-1,3-diene)iron(0) complexes proceeded at 23°C to give putative tricarbonyl(η3-allyl)iron(0) anion complexes. Trapping of the reactive intermediates with bromine produced nucleophilic-substituted tricarbonyl(η4-1,3-diene)iron(0) complexes. 相似文献
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A. Eisenstadt 《Journal of organometallic chemistry》1973,60(2):335-342
Nucleophilic attack of CN− on bicyclo[3.2.1]octadienyl-, bicyclo[3.2.2]- nonadienyl-, and 6,7-benzobicyclo[3.2.2]nonadienyliron tricarbonyl tetrafluoroborates, results in mixed-type complexes containing both σ and π-allyl bonds. The cyano group in the products is located exo to the bicyclic ring.In contrast, the three cations react smoothly with I−; carbon monoxide is displaced to give iron complexes containing covalently-bound halogen. 相似文献
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Graham R. Knox Peter L. Pauson James Rooney 《Journal of organometallic chemistry》1991,420(3):379-386
New substituted η3-allyl(η5-cyclopentadienyl)dicarbonylmanganese cations have been prepared as their tetrafluoroborates. They readily add a wide range of nucleophiles yielding η2-alkene(η5-cyclopentadienyl)dicarbonylmanganese complexes. Of the latter, in general only those involving terminal alkenes are sufficiently stable to permit ready isolation; otherwise metal-free alkenes are obtained. Regioselectivity in these additions depends on the nucleophile. 相似文献
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Andrea GotiMartin F. Semmelhack 《Journal of organometallic chemistry》1994,470(1-2):C4-C7
Arene displacement from the title complex occurs under unprecedented mild conditions in neutral media to afford (η6-arene)tricarbonylchromium complexes. The process is most effective with heteroaromatic compounds: the first synthesis of a tricarbonyl(η6-quinoline)chromium complex and the diastereoselective preparation of a (η6-indole) complex derived from L-tryptophan are reported as representative examples. 相似文献
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Cornelia Borgmann Christian Limberg Elisabeth Kaifer Hans Pritzkow Lszl Zsolnai 《Journal of organometallic chemistry》1999,580(2):10099
The reaction of Mo(η3-C3H4(CH3))(CH3CN)2(CO)2Cl with AgBF4 in THF yields the cationic complex [Mo(η3-C3H4(CH3))(CH3CN)2(CO)2(THF)]+[BF4]−, 1, whose X-ray structure has been determined. Oxo nucleophiles are capable of replacing the weakly bound THF molecule in 1 and under simultaneous loss of CH3CN the resulting complexes aggregate to oligonuclear compounds. Accordingly, the reactions with NaOMe and KOH yield [Na(THF)4]+[(η3-C3H4(CH3))(CO)2Mo(μ-OCH3)3Mo(CO)2(η3-C3H4(CH3))]−, 2 and [K(18-crown-6)]+[[Mo(η3-C3H4(CH3))(CO)2]3(μ2-OH)3(μ3-OH)]−, 3, which were characterized by means of single crystal X-ray diffraction. Due to fluoride abstraction from BF4− the reaction of 1 with KOH also yields fluorinated derivatives of 3 but incorporation of fluorine in 3 can be avoided if AgO3SCF3 rather than AgBF4 is used to generate the cation of 1. For purposes of comparison the dinuclear complex [K(18-crown-6)]+[[Mo(η3-C3H4(CH3))(CO)2]2(μ2-F)3]−, 4, has been prepared, too, showing fluoride bridges and KF bonding. The chemical properties and the structures of these compounds in solution as well as their role as structural models for intermediates during molybdenum oxide catalysed propene oxidation are discussed. 相似文献
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The neutral complexes (η5-C5H5NiXL (X = Cl, L = PPh3 (I); L = PCy3 (II); X = Br, L = PPh3 (III); L = PCy3 (IV); X = I, L = PPh3 (V); L = PCy3 (VI)) have been obtained by treating NiX2L2 with thallium cyclopentadienide. The same reaction in the presence of TlBF4 gives cationic derivatives [(η5-C5H5)NiL2]BF4 (L = 2PPh2Me (VII); L = dppe (VIII)), whereas mononuclear complexes containing two different ligands (L2 = PPh3 + PCy3 (IX)) or dinuclear [(η5-C5H5)Ni(PPh3)]2dppe(BF4)2 (X) are obtained from the reaction of III with TlBF4 in the presence of a different ligand. Reduction of cationic complexes with Na/Hg gives very unstable nickel(I) derivatives (η5-C5H5)NiL2, which could not be isolated purely. Similar reduction of neutral complexes under CO gives a mixture of decomposition products containing [(η5-C5H5)Ni(CO)]2 and nickel(o) carbonyls, whereas in the presence of acetylenes, dinuclear [(η5-C5H5)Ni]2(RCCR′) (R = R′ = Ph; R = Ph, R′ = H) are obtained. 相似文献
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Reaction of [(η-C7H7)Mo(CO)3][PF6] with certain Group V donor ligands afforded monosubstituted complexes [(η-C7H7)Mo(CO)2L][PF6] (L = P(OPh)3, PPh3, PPh2Me, PPhMe2, AsPh3, SbPh3). These were reduced by NaBH4 to the corresponding cycloheptatriene complexes (1-6-η-C7H8)Mo(CO)2L. In addition, the preparation of alkylcycloheptatriene complexes (1-6-η-C7H7R)Mo(CO)2L (R = Me, L = P(OPh)3, PPh3, PPh2Me; R = t-Bu, L = PPh3) is described. Spectroscopic properties, including 13C NMR, are reported. 相似文献
15.
Reaction of [Cp* RuCl2]2 with
-alanine (
-alaH) in methanol at room temperature in the presence of NaOMe yields the complex Na[Cp* RuCl(
-ala)] (1), which contains a five-membered N,O-coordinated chelate ring. The analogous complex Na[Cp* RuCl(
-phe)] (2) is obtained under similar conditions but at 0°C in 90% yield. At temperatures above 20°C both 2 and the η6-coordinated complex [Cp* Ru(
-pheH)]Cl (4) are obtained, with the proportion of the latter increasing with temperature. Compound 4 is obtained in 88% yield by refluxing [Cp* RuCl2]2 and
-phenylalanine (
-pheH) in CH3OH/CH3ONa followed by separation from 2. The analogous ruthenium(II) sandwich complexes 5–10 were obtained from
-tyrosine and
-tryptophane and various derivatives. [Cp* Ru(
-met)] (3), prepared by the reaction of [Cp* RuCl2]2 with
-methionine (
-metH) in CH3OH/CH3ONa, displays N,O,S-coordination. 相似文献
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Kenneth E. Rohly John S. Heffren Bodie E. Douglas 《Journal of mass spectrometry : JMS》1984,19(8):398-402
Complexes of 2,4-pentanedione (acetylacetone, acac), [Cu(acac)2], [VO(acac)2] and [CO(acac)3], and the chromium(III) derivative of 3-methyl-2,4-pentanedione (methylacetylacetone, meac), [Cr(meac)3], the ligands bis(benzoylacetone)ethylenediimine and bis(salicylidene)ethylenediimine, and their cobalt(II), nickel(II) and copper(II) chelates were analysed by laser desorption mass spectrometry (LAMMA) and compared to electron impact (EI) results. The positive ion LAMMA spectra generally reveal mostly small fragments, although metal cationization peaks are seen for most complexes. Negative ion LAMMA produce carbon clusters and some structurally important fragments. 相似文献
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Brette M. Chapin Lauren D. Hughs James A. Golen Arnold L. Rheingold Adam R. Johnson 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(7):m191-m193
The title complex, [Ti(C5H5)(C2H6N)2Cl], exhibits two nearly planar dimethylamide groups oriented approximately perpendicular to each other. The Ti→cyclopentadienyl centroid vector lies nearly in the plane of one of the dimethylamide groups. Long‐range contacts between Ti—Cl and cyclopentadienyl H—C groups give rise to geometric ordering in the extended solid. 相似文献
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The addition of reactive carbanions to (η4‐1,3‐diene)Fe(CO)3 complexes at ?78 °C and 25 °C produced putative homoallyl and allyl anion complexes, respectively. Reaction of the reactive intermediates with 2‐(phenylsulfonyl)‐3‐phenyloxaziridine afforded nucleophilic substituted (η4‐1,3‐diene)Fe(CO)3 complexes. 相似文献