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Quinuclidine complex

As seen in Figure 10a, the C CP/MAS NMR spectrum of the quinuclidine complex shows the expected asymmetry (for instance, different signals for C-8a and C-9a) due to the asymmetric position of the lithium cation relative to the carbon framework in accordance with the X-ray investigation . The observed linewidths are not exceptionally large, and only small effects on the linewidths were observed when Li was substituted by Li, as shown in Figure 10b. [Pg.153]

FIGURE 11. CP/MAS NMR spectra of fluorenyUithium complexes (a) Quinuclidine complex, (b) DEE complex, (c) TMEDA complex and (d) TFIF complex. Reprinted with permission from Reference 128. Copyright 1990 American Chemical Society... [Pg.155]

The quinuclidine complex of Eu(DPM)3 gives rise to a polyhedron consisting of a distorted octahedron formed by six oxygen atoms with quinuclidine nitrogen located above the center of one of the faces, resulting in overall threefold symmetry. The molecular structure [71] of [Eu(DPM)3 quinuclidine] is shown in Fig. 5.10. [Pg.390]

The i.r. and Raman spectra of BX3 (X = F, Cl, Br, I, or H) complexes of l,4-diazabicyclo[2,2,2]octane, dabco, suggest that these (dabco)(BX3)2 complexes have D3h (not D3) symmetry.269 Analogous quinuclidine complexes gave spectra which could be assigned on the basis of C3u symmetry. [Pg.147]

Europium, tris(2,2,6,6-tetramethyl-3,5-heptanedione-quinuclidine)-stereochemistry, 1, 81 Europium complexes... [Pg.127]

Treatment of GaH3(quin) (quin = quinuclidine) with 1 equivalent of the sterically bulky formamidine as shown in Scheme 40 resulted in formation of a monomeric amido-gallane complex containing a monodentate amidinate ligand. Reaction of this species with a second equivalent of the amidine led to displacement of the quinuclidine ligand and formation of a five-coordinate monohydride complex, which could also be prepared directly by a one-pot reaction of GaHsfquin) with the free amidine in a molar ratio of 1 2 ... [Pg.214]

Theoretical studies aimed at rationalizing the interaction between the chiral modifier and the pyruvate have been undertaken using quantum chemistry techniques, at both ab initio and semi-empirical levels, and molecular mechanics. The studies were based on the experimental observation that the quinuclidine nitrogen is the main interaction center between cinchonidine and the reactant pyruvate. This center can either act as a nucleophile or after protonation (protic solvent) as an electrophile. In a first step, NH3 and NH4 have been used as models of this reaction center, and the optimal structures and complexation energies of the pyruvate with NH3 and NHa, respectively, were calculated [40]. The pyruvate—NHa complex was found to be much more stable (by 25 kcal/mol) due to favorable electrostatic interaction, indicating that in acidic solvents the protonated cinchonidine will interact with the pyruvate. [Pg.56]

The first approach applied for [cinchonidine (CD) - a-keto ester] complex was also unsuccessful. In the open conformation CD cannot provide the required steric shielding. In open form either the quinuclidine or the quinoline moiety of CD will interact with the substrate. It has already been demonstrated that the quinuclidine moiety has a crucial role both in the rate acceleration and the induction of ED [13]. [Pg.243]

In earlier kinetic and computer modeling [1,2, 14] the open form of CD (CDopen) was used to illustrate the adsorbed [CD - a-keto ester] complex. In this complex the quinuclidine nitrogen was involved in the interaction with the substrate directly or via a proton bridge. [Pg.244]

We have modelled the [CDopen - methyl pyruvate] complex. The result is shown in Figure 2. In this complex there is no steric hindrance to prevent the free rotation of the substrate around the quinuclidine nitrogen. Thus, in complex shown in Figure 2. there is no preferential stabilization of the substrate. In earlier computer modeling it was suggested that Pt is involved in the stabilization of the [CDopew-a-lfeto ester] complex, i.e. the Pt surface prevent the free rotation of the substrate, however the driving force for enantio-differentiation, i.e. for preferential adsorption of the substrate, was not discussed [14]. [Pg.244]

The conformational analysis of methyl pyruvate shows that it can have two conformers. In the second conformer the two carbonyls are in syn position. The anti-syn conformational change requires 3 kcal. The [CDqIq qJ - methyl pyruvate ] complex ((R) form) was also calculated and shown in Figure 8. In the above complex the "directionality" of the lone pair of electrons of the quinuclidine nitrogen is advantageous for interactions with both the keto and the ester carbonyl groups. [Pg.247]

Amine complexes stabilized with phosphine ligands of the type [AuL(PR3)]+ have been obtained for L = bipy,2310 phen,2310,231 quinoline,23 1 acridine,2311 benzo[h]quinoline,2311 naphthyr-idine (388)2311 2,2 -biquinoline,2311 di-2-pyridyl-ketone,2311 di-2-pyridylamine,2311 2-(2-pyridyl)-benzimidazole, 2311 ferrocenylpyridine, 2-nitroaniline,2312 4-methoxyaniline,2312 NHPh2, 2 NHEt2,2312 NMe3,2312 quinuclidine,2313 NEt3,2314 2-aminothiazoline,2315 histidine,2316... [Pg.1034]

Blackstock, S. C., J. P. Lorand, and J. K. Kochi. 1987. Charge Transfer Interactions of Amines with Tetrahalomethanes. X-ray Crystal Structures of the Donor-Acceptor Complexes of Quinuclidine and Diazabicyclo-[2.2.2]octane with Carbon Tetrabromide. J. Qrg. Chem. 52,1451. [Pg.76]

Spectroscopic and kinetic investigations of the reactions between 4,6-dinitrobenzofuroxan, 4-nitrobenzofuroxan, and tertiary and secondary amines (i.e., l,4-diazabicyclo[2.2.2]octane, quinuclidine, l,8-diazabicyclo[5.4.0]undec-7-ene, and piperidine) indicate the formation of zwitterionic or anionic complexes (Equation 2). The equilibrium between zwitterionic and anionic complexes is discussed (for reaction with piperidine) on the basis of H NMR spectral data, which indicate the presence of anionic complexes arising from the zwitterionic complex by a fast proton departure. The stability and the rate of formation of title complexes are discussed and compared to similar reactions of 1,3,5-trinitrobenzene <2001J(P2)1408>. [Pg.321]

This new process has one unexpected benefit the rates and turnover numbers are increased substantially with the result that the amount of the toxic and expensive 0s04 is considerably reduced (usually 0.002 mole %). The rate acceleration is attributed to formation of an Os04-alkaloid complex, which is more reactive than free osmium tetroxide. Increasing the concentration of 1 or 2 beyond that of 0s04 produces only negligible increase in the enantiomeric excess of the diol. In contrast quinuclidine itself substantially retards the catalytic reaction, probably because it binds too strongly to osmium tetroxide and inhibits the initial osmylation. Other chelating tertiary amines as well as pyridine also inhibit the catalytic process. [Pg.238]

One of the possible ways to stabilize the amine-halonium complexes is to increase the basicity of the amine, bearing in mind that an appropriate one must also not have easily removable P-hydrogens which will lead to oxidation of the amine and formation of an imine. Quinuclidine (pKa of quinuclidinium ion is 11.3 (55)) is 105-106-fold more basic than the pyridines and both the bromonium (10 (36)) and iodonium (11 (57)) BF4 salts have been made and characterized by X-ray crystallography. Interestingly, although the reaction must generally occur as outlined in Figure 7, neither of these ions shows any observable reaction... [Pg.481]

The long known132 electron donor-acceptor complexes between tertiary amines and carbon tetrahahdes are simple systems. Thus, l,4-diaza[2,2,2]bicyclooctane (DABCO) or quinuclidine afford solid complexes with carbon tetrabromide142. [Pg.440]

X-ray crystal analysis indicates that the DABCO/CBiq complex consists of alternating planes of the diamine and carbon tetrabromide in which each acceptor is bound to two donor units. The quinuclidine/CBr4 complex consists of pairs of donor-acceptor systems in which every quinuclidine molecule is bound to only a single molecule of carbon tetrabromide. [Pg.441]

The stoichiometric enantioselective reaction of alkenes and osmium tetroxide was reported in 1980 by Hentges and Sharpless [17], As pyridine was known to accelerate the reaction, initial efforts concentrated on the use of pyridine substituted with chiral groups, such as /-2-(2-menthyl)pyridine but e.e. s were below 18%. Besides, it was found that complexation was weak between pyridine and osmium. Griffith and coworkers reported that tertiary bridgehead amines, such as quinuclidine, formed much more stable complexes and this led Sharpless and coworkers to test this ligand type for the reaction of 0s04 and prochiral alkenes. [Pg.309]

Another issue is validated by the presented X-ray structures This is related to the pseudoenantiomeric character of the tert-butylcarbamates of quinine and quinidine (Figure 1.19a,b). Except for the vinyl on the backside of the quinuclidine ring, both the complexes that are actually diastereomeric to each other actually look like mirror images with regard to conformations and intermolecular interactions as well so that the pseudoenantiomeric experimental chromatographic behavior for DNB-Leu can be rationalized also on the basis of their X-ray crystal structures. [Pg.60]


See other pages where Quinuclidine complex is mentioned: [Pg.858]    [Pg.172]    [Pg.44]    [Pg.221]    [Pg.59]    [Pg.73]    [Pg.84]    [Pg.858]    [Pg.172]    [Pg.44]    [Pg.221]    [Pg.59]    [Pg.73]    [Pg.84]    [Pg.121]    [Pg.94]    [Pg.56]    [Pg.226]    [Pg.244]    [Pg.244]    [Pg.27]    [Pg.239]    [Pg.516]    [Pg.516]    [Pg.136]    [Pg.481]    [Pg.484]    [Pg.442]    [Pg.120]    [Pg.49]    [Pg.50]    [Pg.52]    [Pg.59]    [Pg.64]    [Pg.65]    [Pg.27]   
See also in sourсe #XX -- [ Pg.390 ]




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