63 research outputs found
Koordinationschemie -gebundener Cyclopentadienyl-Chalkogeno-Ether
Coordination Chemistry of rr-Bonded Cyclopentadienyl Chalcogeno Ethers, I. - Chelate Complexes of Pentakis(methylthio)cymantrene with Metal Carbonyls
[C5(SMe)5]Mn(CO)3 (1) reacts with W(CO)5(THF), Mo(CO)4(C7H8), Cr(CO)3(NCMe)3, and Re(CO)4(-C3H5)/HBF4 to yield the monochelate complexes [[C5(SMe)5]Mn(C0)3][M(CO)4] (M = W: 2; M = Mo: 3) and the dichelate complexes [[C5(SMe)5]Mn(CO)3][M(C0)4]2 (M = W: 4; M = Cr: 5; M = Re BFF4 : 6). The reaction with Mo(CO)3(p-xylene) in THF leads via unstable intermediates, which contain coordinated THF, to a mixture of 3 and [[C5(SMe)5]Mn(CO)3][Mo(CO)4]2 (7). The structures of 3 and 4 in the crystal have been determined by X-ray diffraction methods
Stufenweise Synthese und Kristallstruktur von Tricarbonyl[pentakis(methylthio)cyclopentadienyl]-mangan [{C5(SMe)5}Mn(CO)3]
Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes
Treatment of (carbonyl)chloro(meso-tetra-p-tolylporphyrinato)iridium(III), (TTP)Ir(CO)Cl (1), with excess primary amines at 23 °C in the presence of Na2CO3 produces the trans-amine-coordinated iridium carbamoyl complexes (TTP)Ir(NH2R)[C(O)NHR] (R = Bn (2a), n-Bu (2b), i-Pr (2c), t-Bu (2d)) with isolated yields up to 94%. The trans-amine ligand is labile and can be replaced with quinuclidine (1-azabicyclo[2.2.2]octane, ABCO), 1-methylimidazole (1-MeIm), triethyl phosphite (P(OEt)3), and dimethylphenylphosphine (PMe2Ph) at 23 °C to afford the hexacoordinated carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (for R = Bn: L = ABCO (3a), 1-MeIm (4a), P(OEt)3 (5a), PMe2Ph (6a)). On the basis of ligand displacement reactions and equilibrium studies, ligand binding strengths to the iridium metal center were found to decrease in the order PMe2Ph \u3e P(OEt)3 \u3e 1-MeIm \u3e ABCO \u3e BnNH2 ≫ Et3N, PCy3. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a,b), 1-MeIm (4a)) undergo protonolysis with HBF4 to give the cationic carbonyl complexes [(TTP)Ir(NH2R)(CO)]BF4 (7a,b) and [(TTP)Ir(1-MeIm)(CO)]BF4 (8), respectively. In contrast, the carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = P(OEt)3 (5a), PMe2Ph (6a,c)) reacted with HBF4 to afford the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10), respectively. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a–d), 1-MeIm (4a), P(OEt)3 (5b), PMe2Ph (6c)) reacted with methyl iodide to give the iodo complexes (TTP)Ir(L)I (L = RNH2 (11a–d), 1-MeIm (12), P(OEt)3(13), PMe2Ph (14)). Reactions of the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10) with [Bu4N]I, benzylamine (BnNH2), and PMe2Ph afforded (TTP)Ir(PMe2Ph)I (14), (TTP)Ir[P(OEt)3]I (13), [(TTP)Ir(PMe2Ph)(NH2Bn)]BF4 (16), and trans-[(TTP)Ir(PMe2Ph)2]BF4 (17), respectively. Metrical details for the molecular structures of 4a and17 are reported
Group 11 complexes with the 1,1′Bis[N,N′-(2-(diphenylphosphino) amide] ferrocene ligand
ChemInform Abstract: Observation of Anion Spinning in the Dynamic 31P NMR Spectra of Fluorine-Bridged SbF- 6, BF- 4, and PF- 6 Adducts of R3P(CO)3(NO)W+. Implications for Barriers to Ionization and the Formation of Ion Pairs and Free Ions in Methylene Chl
ChemInform Abstract: Coordination of “Noncoordinating” Anions: Synthesis, Characterization, and X-Ray Crystal Structures of Fluorine-Bridged (SbF6)-, (BF4)-, and (PF6)- Adducts of (R3P(CO)3(NO)W)+. An Unconventional Order of Anion Donor Strength.
ChemInform Abstract: Catalysis of Diene Polymerization and Diels-Alder Reactions by an Octahedral Tungsten Nitrosyl Lewis Acid. X-Ray Crystal Structure of the η1-Acrolein Complex (cis-Me3P)(trans-NO)(CO)3W-O=C(H)C(H)=CH2.
ChemInform Abstract: Observation of a Novel 31P NMR cis-Influence Series: Implications for the Relative Basicity of PPh3 and PMe3 in Tungsten Carbonyl Complexes.
Science of Fullerenes and Carbon Nanotubes By M. S. Dresselhaus (MIT), G. Dresselhaus (MIT), and P. C. Eklund (University of Kentucky). Academic Press: San Diego. 1996, xviii + 965 pp. ISBN 0-12-221820-5.
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