Über die Reaktion sekundärer Amine mit Lithiumtetrahydridoaluminat

1988 ◽  
Vol 43 (9) ◽  
pp. 1101-1112 ◽  
Author(s):  
Gerald Linti ◽  
Heinrich Nöth ◽  
Peter Rahm
Keyword(s):  
Nmr Spectroscopy ◽  
Ambient Temperature ◽  
Nmr Spectra ◽  
Substitution Product ◽  
X Ray ◽  
Molar Ratios

Abstract Lithium-tris(diethylamino)hydridoaluminate, Lithium-bis(diisopropylamino)dihydridoaluminate. Lithium(tetramethylpiperidino)trihydridoaluminate, NMR Spectra, X-Ray Reactions of diethylamine, diisopropylamine and 2,2,6,6-tetramethylpiperidine with LiAlH4 in various ethers have been studied. Only two well-defined products result from Et2NH, namely LiAlH(NEt2)- and LiAl(NEt2)4 . If molar ratios of Et2NH:LiAlH4 smaller than 3:1 are employed all compounds of the series LiAlH4-n(NEt2)n (n = 0, 1, 2, 3) are present in solutions of tetra-hydrofuran and diglyme. In diethylether insoluble materials consisting predominantly of lithium diethylaminohydridoaluminates and, presumably, small quantities of Li3AlH6 are also formed. At ambient temperature diisopropylamine reacts slowly with LiAlH4 , and LiAlH2(NiPr2)2 can be isolated as a well-defined substitution product. 2,2,6,6-tetramethylpiperidine (tmpH) replaces only a single hydride from LiAlH4 with formation of LiAlH3 (tmp). The reactions have been monitored by 7Li, 13C and 27Al NMR spectroscopy, and the structure of LiAlH(NEt2)3 has been determined by X-ray analysis. The monoclinic compound contains chains of AlHN3 and LiHN3 tetrahedra linked through common edges.

Metal Tetrahydroborates and Tetrahydroborato Metalates, 15 [1]. An 11B and 113Cd NMR Study of MBH4–CdCl2 Systems in Dimethylformamide and the X-Ray Structure of CdCl2 · 2 DMF

1990 ◽  
Vol 45 (11) ◽  
pp. 1463-1471 ◽  
Author(s):  
Gerald Linti ◽  
Heinrich Nöth ◽  
Martina Thomann
Keyword(s):  
Crystal Structure ◽  
Nmr Spectroscopy ◽  
Coordination Polymer ◽  
Ambient Temperature ◽  
Nmr Spectra ◽  
Carbonyl Oxygen ◽  
X Ray ◽  
Rapid Exchange ◽  
Nmr Study ◽  
In Cis

CdCl2 dissociates in dimethylformamide into the species Cd(DMF)62+, CdCl(DMF)5+ and CdCl3- as determined by 113Cd NMR spectroscopy. 11B and 113Cd NMR spectra of MBH4/CdCl2 solutions in this solvent show the presence of complexes [CdCl2-n(BH4)n+1]- with rapid exchange of BH4- and Cl- at ambient temperature. There is no evidence that Cd(BH4)2 is formed in a metathetical reaction.The crystal structure of CdCl2 · 2 DMF has been determined. It is a coordination polymer containing hexacoordinated Cd atoms with the DMF molecules in cis-position. Coordination of DMF occurs via the carbonyl oxygen atoms.

Unusual Rearrangement of Naphthalene in the Synthesis of a Novel B8-B8-Bridged Derivative in the [(1,2-C2B9H11)2-3-Co]- Series. X-Ray Structure and 11B NMR Spectra of [8,8'-μ-(CH2-C9H6)-(1,2-C2B9H10)2-3-Co]- (CH3)4N+

1997 ◽  
Vol 62 (5) ◽  
pp. 746-751 ◽  
Author(s):  
Andreas Franken ◽  
Jaromír Plešek ◽  
Christiane Nachtigal
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Nucleophilic Substitution ◽  
Nmr Spectra ◽  
X Ray Diffraction ◽  
X Ray ◽  
Unusual Rearrangement ◽  
Multinuclear Nmr Spectroscopy ◽  
11B Nmr ◽  
Isolated Compound

On treatment of the [(1,2-C2B9H11)2Co]- ion with naphthalene in presence of AlCl3 a remarkably bridged [8,8'-μ-(CH2-C9H6)-(1,2-C2B9H10)2-3-Co]- ion is obtained as a single isolated compound. The triatomic -CH2-C9H6- bridge is derived from the rearranged naphthalene nucleus. The mechanism of this reaction is obscure but it does resemble the "Electrophile-Induced Nucleophilic Substitution" reported earlier. The structure of the compound was established by multinuclear NMR spectroscopy and by single crystal X-ray diffraction.

Nuclear magnetic resonance studies on the anions [M(SnCl3)5Cl]4− (M = Ru, Os) and [Ru(SnCl3)5(MeCN)]3−: the X-ray crystal structure of [N(C2H5)4]4[Ru(SnCl3)5Cl]

1982 ◽  
Vol 60 (11) ◽  
pp. 1304-1316 ◽  
Author(s):  
Louis J. Farrugia ◽  
Brian R. James ◽  
Claude R. Lassigne ◽  
Edward J. Wells
Keyword(s):  
Crystal Structure ◽  
Nuclear Magnetic Resonance ◽  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Octahedral Geometry ◽  
Coupling Constants ◽  
Order Effects ◽  
Magnetic Resonance Studies ◽  
X Ray ◽  
Crystallographic Study

The octahedral anions [M(SnCl3)5Cl]4− (M = Ru, Os) have been fully characterized by 119Sn FT nmr spectroscopy. For M = Ru, 117Sn and 115Sn nmr spectra were also recorded, and an X-ray crystallographic study was carried out on the tetraethylammonium salt, isolated as a disolvate from acetonitrile. The Ru—Sn bond lengths indicate some degree of dπ–dπ interactions. The slight distortions from octahedral geometry are discussed in connection with the packing of the chlorine atoms. The Sn nmr spectra reveal the first observed coupling to a 99Ru nucleus (I = 5/2, 12.7% natural abundance), very large 2J(119Sn—117Sn) coupling constants, and the first observed second-order effects on a heteronuclear system. The octahedral anion [Ru(SnCl3)5(MeCN)]3− was also synthesized as the tetraethylammonium salt and characterized spectroscopically.

Oligophosphan-Liganden, XX [1] Reduktion von CO2 am Trisphosphanrhodium(I)-Komplex RhCl[t-BuP(CH2CH2CH2PMe2)2] Oligophosphine Ligands, X X [1] Reduction of Carbon Dioxide by the Trisphosphinerhodium (I) Complex RhCl[t-BuP(CH2CH2CH2PMe2)2]

1986 ◽  
Vol 41 (6) ◽  
pp. 718-721 ◽  
Author(s):  
Lutz Dahlenburg ◽  
Constanze Prengel ◽  
Nils Höck
Keyword(s):  
Carbon Dioxide ◽  
Nmr Spectroscopy ◽  
Structure Analysis ◽  
Nmr Spectra ◽  
X Ray

The reaction of Rh2Cl2(cyclo-C8H 12)2 with t-BuP(CH2CH2CH2PMe2)2 gave RhCl[t-BuP(CH2CH2CH2PMe2)2] (1) which was characterized by its 1H and 31P NMR spectra. 1 interacted with carbon dioxide to produce Rh(O2CO)Cl[t-BuP(CH2CH2CH2PMe2)2](2) and CO. 2 was studied by IR and 13C and 31P NMR spectroscopy as well as by an X-ray structure analysis. There is no evidence for any production of carbon dioxide derivatives containing C- or C- and O- bound integer CO2 ligands.

Komplexe des Typs [MCl4(SEt2)2] mit M = Mo und W. Kristallstrukturen, NMR-Spektren und magnetisches Verhalten/[MCl4(SEt2)2] Complexes with M = Mo and W. Crystal Structures, NMR Spectra, and Magnetic Behaviour

1995 ◽  
Vol 50 (2) ◽  
pp. 159-167 ◽  
Author(s):  
Peter Dierkes ◽  
Gerlinde Frenzen ◽  
Sigrid Wocadlo ◽  
Werner Massa ◽  
Stefan Berger ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Nmr Spectra ◽  
Magnetic Behaviour ◽  
Triclinic Space Group ◽  
Magnetic Susceptibilities ◽  
X Ray ◽  
Metal Atoms ◽  
Ray Methods ◽  
C Nmr

The crystal structures of the thioether complexes [MCl4(SEt2)2] with M = Mo and W have been solved by X-ray methods. Both compounds crystallize isotypically in the triclinic space group P1̄ with two formula units per cell unit. The metal atoms are octahedrally coordinated by four chlorine atoms and by the two sulfur atoms of the thioether molecules in transposition (symmetry Ci) with bond lengths (average): Mo-Cl 233.1, Mo-S 253.4, W-Cl 233.1, and W-S 251.7 pm. Both complexes were also characterized by 1H and 13C NMR spectroscopy as well as by measurement of the magnetic susceptibilities in the temperature range from 1.8 to 350 K.

scholarly journals Palladium(II) complexes with R2edda derived ligands, Part III: Diisobutyl (s,s)-2,2'-(1,2-ethanediyldiimino)di(4-methylpentanoate) and its palladium(II) complex: Synthesis and characterization

2009 ◽  
Vol 74 (11) ◽  
pp. 1249-1258 ◽  
Author(s):  
Bojana Zmejkovski ◽  
Goran Kaludjerovic ◽  
Santiago Gómez-Ruiz ◽  
Tibor Sabo
Keyword(s):  
Crystal Structure ◽  
Nmr Spectroscopy ◽  
Hydrogen Bonds ◽  
Nmr Spectra ◽  
Symmetry Axis ◽  
Layer Structure ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ir And Nmr Spectroscopy

A new R2edda-type ester, diisobutyl (S,S)-2,2'-(1,2-ethane-diyldiimino) di(4-methylpentanoate) dihydrochloride, [(S,S)-H2iBu2eddl]Cl2, 1, and its palladium(II) complex, dichloro(diisobutyl (S,S)-2,2'-(1,2-ethanediyldiimino) di(4-methylpentanoate))palladium(II), [PdCl2{(S,S)-iBu2eddl}], 2, were synthesized and characterized by elemental analysis, as well as IR and NMR spectroscopy. It was found that complex 2 was obtained as mixture of two diastereoisomers, observed in NMR spectra. The crystal structure of compound 1 was determined by X-ray diffraction studies and is described. The isolated crystals consisted of one dicationic species [(S,S)-H2iBu2eddl]2+ and two Cl-. The crystal system was tetragonal with the space group P42. Hydrogen bonds significant for the manner of packing are N-H1N???Cl, 3.049(3) ?, 159(3)? and N-H2N???Cl, 3.100(3) ?, 164(3)?. An infinite chain was formed building a one layer structure, usual for these types of compounds. The C2 symmetry axis of the compound passes through the C1-C1i bond vector and lies perpendicular to the plane N2Cl2.

Synthesis of Sterically Demanding Bis(phosphinimine) Dibenzofuran Ligands and Subsequent Zinc Metalation

2015 ◽  
Vol 68 (3) ◽  
pp. 373 ◽  
Author(s):  
Matthew T. Zamora ◽  
Saif M. Zahir ◽  
Kevin R. D. Johnson ◽  
Clay J. Barnson ◽  
Craig A. Wheaton ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Ambient Temperature ◽  
Elemental Analysis ◽  
Elimination Reaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Multinuclear Nmr ◽  
Sterically Demanding ◽  
Multinuclear Nmr Spectroscopy ◽  
Alkane Elimination

In light of previous success surrounding the use of bis(phosphinimine)dibenzofuran ligands for zinc-mediated lactide polymerization, a series of sterically demanding P=N pincer compounds have been prepared with important steric and electronic modifications at both P- and N-sites (L, 3a–d). These systems are highly crystalline and have been extensively characterized using multinuclear NMR spectroscopy, elemental analysis, and X-ray diffraction. The ligands can be transformed into their protonated analogues [HL][BArF4] (4a–d, [BArF4] = [B(m-(CF3)2-C6H3)4]) by reaction with Brookhart’s acid, and subsequently coordinated to zinc via an alkane elimination reaction with [ZnEt2] at ambient temperature to afford the corresponding [LZnEt][BArF4] cationic complexes 5a–d. In addition, an unusual chloridozinc species [LZnCl][BArF4] (5c′) has been isolated and structurally characterized, providing comparisons to previously established ligand sets with similar geometries.

Coordination Behavior of tBu2PH towards [{Rh(μ-Cl)(coe)2}2] (coe = cis-cyclooctene): Crystal and Molecular Structure of [{Rh(μ-Cl)(tBu2PH)2}2]

2008 ◽  
Vol 63 (9) ◽  
pp. 1035-1039 ◽  
Author(s):  
Hans-Christian Böttcher ◽  
Peter Mayer
Keyword(s):  
Molecular Structure ◽  
Nmr Spectroscopy ◽  
Crystal And Molecular Structure ◽  
Molar Ratio ◽  
X Ray ◽  
X Ray Crystallography ◽  
Molar Ratios ◽  
H Nmr ◽  
Coordination Behavior ◽  
Independent Synthesis

The reaction of [{Rh(μ-Cl)(coe)2}2] (coe = cis-cyclooctene) with tBu2PH in different solvents in various molar ratios was investigated. Working with a molar ratio of Rh to P = 1 : 2 in heptane overnight afforded [{Rh(μ-Cl)(tBu2PH)2}2] (1) in nearly quantitative yield. Upon tuning the molar ratio (Rh/P) in the range from 1 : 2 to 1 : 0.5, 31P{1H} NMR spectroscopy indicated the formation of [(tBu2PH)2Rh(μ-Cl)2Rh(coe)2] (3) besides the complexes [{Rh(μ-Cl)(coe)(tBu2PH)}2] (cis, 2a; trans, 2b). The constitution of 3 was established by an independent synthesis mixing 1 with [{Rh(μ- Cl)(coe)2}2] or [{Rh(μ-Cl)(cod)}2] (cod = 1.4-cyclooctadiene), respectively, which also yielded [(tBu2PH)2Rh(μ-Cl)2Rh(cod)] (4). Single crystals of 1 have been analyzed by X-ray crystallography (monoclinic, Cc, Z = 8, a = 32.7375(3), b = 11.1294(1), c = 24.5134(3)Å ; β = 106.7228(4)◦; V = 8553.70(15) Å3; T = 200 (2) K).

scholarly journals Synthesis of Molybdenum Blue Dispersions Using Ascorbic Acid as Reducing Agent

2020 ◽  
Vol 4 (2) ◽  
pp. 24 ◽  
Author(s):  
Natalia Gavrilova ◽  
Maria Myachina ◽  
Daria Harlamova ◽  
Victor Nazarov
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Ascorbic Acid ◽  
Nmr Spectroscopy ◽  
Photoelectron Spectroscopy ◽  
Reducing Agent ◽  
Ammonium Heptamolybdate ◽  
X Ray ◽  
Molybdenum Blue ◽  
Molar Ratios ◽  
Nanoparticles Dispersions

Stable molybdenum blue nanoparticles dispersions were synthesized using ammonium heptamolybdate and ascorbic acid. The effect of molar ratios of reducing agent/Mo and acid/Mo on the speed of formation and stability of the disperse system has been demonstrated. The particles were characterized by UV/vis, infrared (FTIR), nuclear magnetic resonance (NMR) spectroscopy, and dynamic light scattering (DLS) methods. The X-ray photoelectron spectroscopy (XPS) method confirmed the presence of reduced MoV in the structure of molybdenum oxide nanoclusters, the proportion of which was 30%.

Structure of Supercooled Aqueous Zinc(II) Bromide Solutions by Raman and X-Ray Scattering Methods

1992 ◽  
Vol 47 (7-8) ◽  
pp. 841-848
Author(s):  
Toshiyuki Takamuku ◽  
Kazumasa Yoshikai ◽  
Toshio Yamaguchi ◽  
Hisanobu Wakita
Keyword(s):  
Raman Spectroscopy ◽  
Ambient Temperature ◽  
Raman Spectra ◽  
Glassy State ◽  
X Ray ◽  
Molar Ratios ◽  
Main Species ◽  
X Ray Scattering ◽  
Bromide Solutions ◽  
Ray Scattering

Abstract The structure of aqueous zinc(II) bromide solutions with [H2O/[ZnBr2] molar ratios 5 and 10 in the supercooled state and at ambient temperature has been investigated by Raman spectroscopy and X-ray scattering. Raman spectra of glassy solutions have also been measured for comparison. The Raman and X-ray data suggest that tetrabromo and hexaaqua zinc(II) complexes are favoured in the supercooled and glassy state, while dibromo- and tribromozinc(II) complexes are formed as main species in the solutions at ambient temperature. Probably the reactions and occur in the supercooled and glassy solutions. These equilibrium shifts are discussed.

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