15N-NMR Spectroscopy. XVIII. Sequence Analysis of Linear Polyureas

Various homo- and copolyureas were prepared either by conversion of diamines with diisocyanates or by heating diamines with N, N'-bisphenoxycarbonyl diamines. The ¹³C-NMR spectra and the natural abundance ¹⁵N-NMR spectra were measured in trifluoroacetic acid. In contrast to polyamides, the carbonyl signals of polyureas are not sensitive to neighboring residue effects, so that ¹³C-NMR spectra are in most cases useless for the sequence analysis of copolyureas. The ¹⁵ N-NMR signals of urea groups are, however, sensitive to the influence of both substituents and thus contain information on the sequence. Structure/ shift-relationships are discussed, and ¹⁵ N-NMR spectra of various copolyureas are presented.     

15N-NMR. Studies of Aminopyridines,Aminopyrimidines and of Some Diazine N-Oxides

¹⁵N-NMR. spectra of mono- and diaminopyridines, and mono-, di- and triaminopyrimidines including trimethoprim and other dihydrofolate reductase inhibitors have been studied in neutral and acidic media. Complete chemical shift assignments are given. Ring-nitrogen shifts are discussed in terms of β-, χ- and δ-substituent effects of amino and alkyl groups. Protonation states in TFA- and FSO₃H-solution and protonation increments for the ¹⁵N-shifts of ring and amino N-atoms are determined. A linear correlation is observed between amino substituent effects (Δδ(¹⁵N)) on the ring N-atom in aminopyridines and corresponding Δδ (¹³C) values in aminobenzenes and, similarly, between Δδ(¹⁵N) values in aminopyrimidines and Δδ(¹³C) values in aminopyridines. Assignment of the ¹⁵N-NMR. spectra of pyrimidine N-oxides, pyrazine N-oxides and pyridazine N-oxides is achieved by comparison with ¹⁴N-NMR. data and with the aid of Yb(fod)₃-induced shifts. One-bond ¹⁵N, ¹H-coupling constants are reported for aminopyridines and aminopyrimidines and discussed in terms of conjugative interaction between NH₂-group and ring system.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [Pt(N3)6]2– und [Pt(N3)Cl5]2–, 195Pt‐ und 15N‐NMR‐Spektren von [Pt(N3)nCl6–n]2– und [Pt(15NN2)n(N215N)6–n]2–, n = 0–6

Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N₃)₆]^2– and [Pt(N₃)Cl₅]^2–, ¹⁹⁵Pt and ¹⁵N NMR Spectra of [Pt(N₃)_nCl_6–n]^2– and [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 By ligand exchange of [PtCl₆]^2– with sodium azide mixed complexes of the series [Pt(N₃)_nCl_6–n]^2– and with ¹⁵N‐labelled sodium azide (Na¹⁵NN₂) mixtures of the isotopomeres [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 and the pair [Pt(¹⁵NN₂)Cl₅]^2–/[Pt(N₂¹⁵N)Cl₅]^2– are formed. X‐ray structure determinations on single crystals of (Ph₄P)₂[Pt(N₃)₆] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph₄As)₂[Pt(N₃)Cl₅] · HCON(CH₃)₂ ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with N^α–N^β–N^γ‐angles = 173.5–174.6° are bonded with Pt–N^α–N^β‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu₄N)₂[Pt(N₃)Cl₅] are observed at 318–345, the PtN stretching modes of (n‐Bu₄N)₂[Pt(N₃)₆] at 401–428 and of (n‐Bu₄N)₂[Pt(N₃)Cl₅] at 408–413 cm^–1. The mixtures (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 and (n‐Bu₄N)₂[Pt(¹⁵NN₂)Cl₅]/(n‐Bu₄N)₂[Pt(N₂¹⁵N)Cl₅] exhibit ¹⁵N‐isotopic shifts up to 20 cm^–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are f_d(PtCl) = 1.93, f_d(PtN^α) = 2.38 and f_d(N^αN^β, N^βN^γ) = 12.39 mdyn/Å. In the ¹⁹⁵Pt NMR spectrum of [Pt(N₃)_nCl_6–n]^2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The ¹⁵N NMR spectrum of (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 exhibits by ¹⁵N–¹⁹⁵Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal ¹⁵N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.     

Über Pterinchemie. 79. Mitteilung. 13C-und 15N-NMR.-spektroskopische Untersuchungen an der (6RS)-5, 10-Methylen-5, 6, 7, 8-tetrahydro-L-folsäure; eindeutiger Beweis ihrer Struktur

¹³C- and ¹⁵N-NMR.-Spectroscopic Studies on (6RS)-5, 10-Methylene-5, 6, 7, 8-tetrahydro-L -folic Acid; Unequivocal Proof of thier Structure The existence of a 5, 10-methylene bridge in the title compound has been established with the help of ¹⁵N-NMR, and ¹³C-NMR. spectroscopy. The simultaneous coupling of ¹³C(11) with ¹⁵N(5) and ¹⁵N(10) proves that C(11) must be bound as a methylene bridge to both N-atoms. Some other aspects of the NMR. spectra of the compound are discussed. Synthesis of the title product with the label ¹⁵N is described.     

Nitrogen-15 nuclear magnetic resonance spectroscopic study of compounds with nitrogen?nitrogen bonds

The ¹⁵N NMR spectra of several substances with nitrogen—nitrogen bonds have been obtained at the natural-abundance level by high-resolution NMR spectroscopy. Azo (? N?N? ) nitrogens are 300–500 ppm deshielded compared with hydrazo (? NH? NH? ) nitrogens. The sensitivity of the ¹⁵N shifts in these types of substances to substituent changes are reported, along with ¹⁵N–¹H spin–spin couplings for some hydrazo compounds. Hydrogen-bonding effects arising from solvent changes on the ¹⁵N shifts of azoxybenzene are different for its two kinds of nitrogen. The ¹⁵N NMR spectrum of N,N'-dinitrosopiperazine in dimethyl sulfoxide at room temperature is consistent with the presence of two different conformations about the N? NO bonds.     

Peptide conformations. Part 30. Assignment of the 1H-, 13C-, and 15N-NMR spectra of cyclosporin A in CDCl3 and C6D6 by a combination of homo- and heteronuclear two-dimensional techniques

The ¹H-, ¹³C-, and ¹⁵N-NMR spectra of the immunosuppressive cyclic undecapeptide cyclosporin A ( 1 ) have been analyzed at 300 MHz in CDCl₃, C₆D₆, and mixtures of these solvents. A combination of different homo- and heteronuclear two-dimensional NMR techniques enable complete assignment of all H-, C- and 4 N-signals. Recognition of the proton spin systems has been achieved via ¹H,¹H–COSY and double-quantum-¹H-NMR spectroscopy. NOESY spectra yield some sequence assignments, but two techniques using coupling across amide bonds have been applied to get independent assignments of all amino acids in the sequence: (i) An ¹H,¹H-COSY spectrum optimized for small coupling constants enables the detection of long-range couplings from N-methyl groups to both α-protons attached to that amide bond. (ii) An ¹H, ¹³C-COSY spectrum optimized for C,H-long-range couplings (J = 5 to 10 Hz) to the eleven CO groups again yields coupling to both α-protons attached to that amide bond. Additionally these two experiments yield the assignment of N-methyl protons and carbonyl C-atoms. Normal and relayed ¹H,¹³C-COSY in both solvents have been applied to assign all C-atoms via their directly attached and remote protons. An ¹H,¹³C-COLOC spectrum at 500 MHz in CDCl₃, which uses H,C-long-range couplings confirms the assignment of all proton spin systems as well as the C-signals of each individual amino acid. Ambiguities in the assignment of the C(δ)'s of MeLeu have thus been removed. An ¹H,¹⁵N-COSY spectrum enables the assignment of the 4 NH N-atoms.     

13N-NMR spectroscopy. XXXV. Sequence analysis of alternating and random copolyamides made up of aliphatic and aromatic ω-amino acids

Alternating copolyamides of various ω-amino acids were synthesized by base-catalyzed polycondensation of N-isothiocyanatoacyl ω-amino acids in solution. Derivatives of the following amino acids were used: glycine, β-alanine, γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, D ,L -β-aminobutyric acid, trans-4-aminocyclohexane 1-carboxylic acid, 4-aminophenyl acetic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-4-methyl benzoic acid, and 4-amino-3-methyl benzoic acid. The base-catalyzed polycondensation at lower temperatures gave purer products than the bulk condensation at 180–200°C. ¹³C-NMR and natural-abundance ¹⁵N-NMR spectra measured in trifluoroacetic acid demonstrate that in most cases undisturbed alternating sequences were obtained. Strong neighboring residue effects and long-range sequence effects were found in the ¹⁵N-NMR spectra, and structure/shift relationships are discussed. The sequences of copolyamides obtained by copolymerizations of lactams or β-amino acid N-carboxyanhydrides were investigated by both ¹⁵N-NMR and ¹³C-NMR spectroscopy. ¹³C-NMR spectroscopy was found to be more useful if the copolyamides consist of ω-amino acid units of different chain length. However, ¹⁵N-NMR spectroscopy is more suited if the monomer units differ exclusively by their substituents.     

Nitrogen-15 n.m.r. studies of 13C, 15N labeled arginine

¹⁵N n.m.r. spectra of [¹³C-2, 3-¹⁵N₂-guanidino]arginine and [¹³C, ¹⁵N₂] urea were obtained in D₂O and H₂O at a variety of pH values both with and without proton decoupling. The effects of the proton exchange rate are readily observable in the proton coupled ¹⁵N spectra. When the guanidino group is deprotonated (pK = 12.5), the terminal nitrogens give a single resonance 6.6 ppm downfield of the protonated species, indicating a rapid tautomeric exchange. The observed NH and CN couplings are compared with calculated values, and good agreement is found for ¹J(CN) using a Blizzard–Santry type calculation. The ramifications of the proton exchange on ¹⁵N n.m.r. spectra of amino acids and peptides are discussed.     

Triaziridine 7. Mitteilung. Stabile pyramidale Konfigurationen an den Stickstoff-Atomen von Dialkyl-und Trialkyl-triaziridinen

Stable Pyramidal configurations at the Nitrogen Atoms of Dialkyl-and Trialkyl-triaziridines Stereochemical features of the recently synthesized nine samples of di- and trialkyl-triaziridines, namely the 1,3-cyclopentylen-(series a ) and the two stereoisomers of the diisopropyl derivatives (series b and c ), containing as the third substituent an H-atom ( 2 ), a CH₃ group ( 3 )or a CH₂OH group ( 4 ), were elaborated on the basis of the ¹H-, ¹³C-, and ¹⁵N-NMR spectra. The three N-atoms of the saturated N₃-homocycle were found to be stable to pyramidal inversion in all cases. According to their NMR spectra, 2 – 4 of the series a and b possess twofold symmetry (C_s), while 2 – 4 of series c are asymmetric. Thus, series c has the trans-configuration at N(2)/N(3) and, consequently, the cis-configuration at N(1)/N(2), while series a and b have the cis-configuration at N(2)/N(3) and -since the all-cis-arrangement is excluded-the trans-configuration at N(1)/N(2). The asymmetry of the trans-configurated 2c turned into twofold symmetry (C₂), when a little CF₃COOH was added. The ¹H- and ¹³C-NMR data of series b and c of our alkyl-triaziridines exhibit a shielding effect, according to which there are two types of i-Pr groups, i-Pr(a) and i-Pr(b). They differ in the NMR signals of the H- and the C-atoms of their CH groups: the H-atoms of i-Pr(a) are more deshielded by 0.75–1.111 ppm and its C-atoms are more shielded by 10.0–160.0 ppm as compared to the corresponding atoms of i-Pr(b). i-Pr(a) is cis (on the N₃-homocycle) to a large substituent (such as i-Pr, Me, CH₂OH) and to a lone pair, while i-Pr(b)is cis only to a small (H) or to no substituent and to one or two lone pairs. An analogous effect appears in the NMR signals of the CH₃ and CH₂OH groups at N(1) of 3 and 4 in the series b and c .     

Fourier transform NMR investigations of organotin compounds : VIII. Propenyl- and isopropenyl-tin compounds; detection and identification of isomers using 119Sn and 13c NMR

Starting from the equilibrium mixture of cis- and trans-1-bromo-1-propene, isomeric mixtures of compounds Me_n Sn(CH=GHMe)_4-n (n = 0–3) have been prepared and studied. While proton NMR only allows distinction between the methyltin signals of the various isomers (except where n = 3), the ¹³C spectra show separate signals for almost all isomeric carbons even when n = 0. In the ¹¹⁹Sn spectra the signals due to the various isomers are separated by ca. 20 ppm for a given value of n; the peak areas can be used to estimate the proportions of cis- and trans-propenyl residues present in the mixtures. Addition of 2-bromo-propene to the starting 1-bromo-1-propenes leads to the formation of further isomers, which can in all cases be observed and identified in the ¹¹⁹Sn spectra; ¹¹⁹Sn shifts can be calculated using the shifts for the Me₃SnC₃H₅ isomers as increments.     

Computational NMR Spectroscopy of Transition‐Metal/Nitroimidazole Complexes: Theoretical Investigation of Potential Radiosensitizers

The computed chemical shifts of transition‐metal complexes with dimetridazole (= 1,2‐dimethyl‐5‐nitro‐1H‐imidazole; 1 ), a prototypical nitro‐imidazole‐based radiosensitizer, are reported at the GIAO‐BP86 and ‐B3LYP levels for BP86/ECP1‐optimized geometries. These complexes comprise [MCl₂( 1 )₂] (M = Zn, Pd, Pt), [RuCl₂(DMSO)₂( 1 )₂], and [Rh₂(O₂CMe)₄( 1 )₂]. Available δ(¹H) and δ(¹⁵N) values, and Δδ(¹H) and Δδ(¹⁵N) coordination shifts are well‐reproduced theoretically, provided solvation and relativistic effects are taken into account by means of a polarizable continuum model and suitable methods including spin–orbit (SO) coupling, respectively. These effects are particularly important for the metal‐coordinated N‐atom, where the contributions from solvation and relativity can affect δ(¹⁵N) and Δδ(¹⁵N) values up to 10–20 ppm. The ¹⁹⁵Pt chemical shifts of cis‐ and trans‐[PtCl₂( 1 )₂] are well‐reproduced using the zero‐order regular approximation including SO coupling (ZORA‐SO). Predictions are reported for ⁹⁹Ru and ¹⁰³Rh chemical shifts, which suggest that these metal centers could be used as additional, sensitive NMR probes in their complexes with nitro‐imidazoles.     

Analysing the isotopic life history of the alpine ungulates Capra ibex and Rupicapra rupicapra rupicapra through their horns

The horn of ungulate grazers offers a valuable isotopic record of their diet and environment. However, there have been no reports of the spatio‐temporal variation of the isotopic composition of horns. We investigated patterns of carbon (δ¹³C) and nitrogen (δ¹⁵N) isotopic composition along and perpendicular to the horn axis in Capra ibex and Rupicapra rupicapra rupicapra to assess the effects of animal age, within‐year (seasonal) and inter‐annual variation, natural contamination and sampling position on horn isotope composition. Horns of male C. ibex (n = 23) and R. r. rupicapra (n = 1) were sampled longitudinally on the front (only R. r. rupicapra) and back side and on the surface and sub‐surface. The sides of the R. r. rupicapra horn did not differ in δ¹³C. In both species, the horn surface had a 0.15‰ lower δ¹³C and a higher carbon‐to‐nitrogen (C/N) ratio than the sub‐surface. Washing the horn with water and organic solvents removed material that caused these differences. With age, the δ¹⁵N of C. ibex horns increased (+0.1‰ year^?1), C/N ratio increased, and ¹³C discrimination relative to atmospheric CO₂ (¹³Δ) increased slightly (+0.03‰ year^?1). Geostatistical analysis of one C. ibex horn revealed systematic patterns of inter‐annual and seasonal ¹³C changes, but ¹⁵N changed only seasonally. The work demonstrates that isotopic signals in horns are influenced by natural contamination (δ¹³C), age effects (¹³Δ and δ¹⁵N), and seasonal (δ¹³C and δ¹⁵N) and inter‐annual variation (δ¹³C). The methods presented allow us to distinguish between these effects and thus allow the use of horns as isotopic archives of the ecology of these species and their habitat. Copyright © 2009 John Wiley & Sons, Ltd.     

Solvent-Induced Deuterium Isotope Effects in 13C- and 15N-NMR. Spectra of Enaminones

The effect of deuterium on the ¹³C and ¹⁵N chemical shifts of enaminones has been investigated. D/H isotope shifts are reported for neutral and protonated species, i.e., when the isotope is exchanged on the C(2)-, N-, or O-atoms. In cases of slow exchange the isotope shifts were obtained from solutions containing both isotopomers, whereas for fast exchange (acidic solutions) either separate NMR. sample tubes (¹⁵N-NMR.) or coaxial tubes (¹³C-NMR.) were used. In neutral molecules the isotope effects δ_C(D, H) are intrinsic in nature. In acidic solutions, the enaminocarbonyl cations formed exhibit δ_C(D, H)- and δ_N(D, H)-values which are discussed in terms of the proton transfer. The mesomeric character of the cations is reflected by characteristic features in the δ_C(D, H)- and δ_N(D, H)-values, which can be ascribed to isotopic perturbation of resonance. O-Protonation shifts in the ¹⁵N-resonance, observed for the first time, are large and positive (+60 to +76 ppm), in contrast to amides, where the effects are of the same sign but an order of magnitude smaller. Both protonation shifts and solvent-induced isotope effects are discussed in connection with the nucleophilic character of the reactive centers in the enaminone synthon.     

Triaziridine. 4. Mitteilung. Synthese von cis-2,3-Diisopropyltriaziridin-1-carbonsäureestern

Triaziridines. Synthesis of cis-2,3-Diisopropyltriaziridine-1-carboxylic Esters Irradiation of the (Z)-azimines 1a , b in Et₂O with a Hg high pressure lamp through Corex yielded (besides 30% of the previously described trans-triaziridines 3a , b ) 15% of the new cis-triaziridines 4a , b . The same irradiation of the (E)-azimines 2a , b afforded only 15–18% of 3a , b but 20–23% of 4a , b . Thus, these azimine photocyclizations show some stereospecificity. The triaziridines 3a , b and 4a , b formed in this way were always accompanied by the same three types of by-products, namely 10–15% of the ‘triazones’ 5a , b , 11–20% of the carbamic esters 6a , b , and 5–10% of the ether/nitrene insertion products 7a , b . The constitution and configuration of the new cis-triaziridines 4 followed from their spectral properties. Of particular interest are the symmetry properties of 4 derived from the ¹H-, ¹³C-, and ¹⁵N-NMR spectra: The stereoisomers 3 and 4 differ only in that the isochronicity of the two constitutionally equivalent molecular halves is temperature dependent in 3 but independent in 4 . Both triaziridines 3 and 4 exhibit the IR CO band at (for carbamates) remarkably high frequency. The results confirm that the alkyl-substituted N-atoms of triaziridines are pyramidally stable, that the corresponding acyl-substituted N-atoms (N(1)) are also pyramidal, but can invert more readily, and that rotation around the N(1), C(?O) bond is rapid. Thus, there can be only little amide-type delocalization between a triaziridine N-atom and an acyl substituent of the carbamate type attached to it.     

NMR-spektroskopische Untersuchungen an Mercaptophosphazenen. II. NMR-spektroskopische Untersuchungen an 15N-markierten Mercaptophosphazenen

N.M.R. Spectroscopic Investigations of Thiophosphazenes. II. N.M.R. Spectroscopic Investigations of ¹⁵N Labelled Thiophosphazenes Completely ¹⁵N labelled compounds of the type ¹⁵N₃P₃Cl_6?n(SR)_n, R = Et or Ph; n = 0, 2, 4, or 6, and of the type ¹⁵N₄P₄Cl_8?n(SR)_n, R = Et; n = 0, 4, or 8, were prepared and investigated by means of both ³¹P n.m.r. spectroscopy and ¹⁵N n.m.r. spectroscopy respectively. The coupling constants ²J_PP, in some cases only found by simulating the spectra, and the coupling constants ¹J_PN are given. The values of these coupling constants and their relation are discussed. The general tendency is visible, that with increasing coupling constant ¹J_PN the coupling constant ²J_PP decreases. With increasing grade of substitution n the ¹⁵N chemical shifts are changed to higher fields.     

Metalla- und Phosphaheterocyclen mit Diamino-Supermesitylboryl-Einheiten

Metalla- and Phosphaheterocycles with Diaminosupermesitylboryl Units RB(NMeLi)₂ is reacted with dimethylmetaldichlorides to give four membered (n = 1) metallacycles of the type (? RB? NMe? MMe₂? NMe? )_n (M = Si, IIa ; M = Ge, IIb ) and the eight membered ring (n = 2) with M = Sn, III . The four membered ring (? RB? NMe? PCMe₃? NMe? ), IV , is formed with Me₃CPCl₂. RBF₂ and lithiated N,N′-dimethylethylenediamine give the five membered ring RB(? NMe? CH₂—)₂, Va . The reaction of RB(NHMe)₂ with trimethylaluminum upon elimination of methane yields the symmetrical eight membered ring system (? RB? NMe? AlMe? NMe? )₂, VI . The compounds are characterized by their m.s. and n.m.r. (¹H, ¹¹B, ¹³C, ²⁹Si, ³¹P, ¹¹⁹Sn and in part ¹⁵N) spectra, and with the exception of III and VI also by elemental analyses. An X-ray structure analysis is provided for III .     

Tetrazoloazines. 15N nuclear magnetic resonance and infrared absorption spectroscopy

The reaction of 4-chloro-2-phenylquinazoline with K¹⁵NN₂ has been studied by ¹⁵N-NMR. spectroscopy. ¹⁵N-chemical shifts in 5-phenyl-1 (3)-[¹⁵N]-tetrazolo[1,5-c]quinazoline and -Nα(Nγ)-[¹⁵N]-4-azido-2-phenylquinazoline are reported. The characteristic IR. absorption frequencies of the tetrazole group have been determined in a series of annelated ¹⁵N-labelled compounds. From these studies and the chemistry of the labelled tetrazoles, it is concluded that all haloazines examined react with KN₃ by the direct nucleophilic substitution mechanism. An addition of nucleophile-ring opening-ring closure (ANRORC) mechanism was not observed. The synthesis of several ¹⁵N-labelled tetrazoloazines is described.     

Bestimmung der Struktur von Phenyläthinyllithium in Lösung mittels Tieftemperatur-NMR-Spektroskopie

The dimeric and tetrametic structures of complexes of phenylethinyllithium, as recently discovered by X-ray analysis in the solid state, were also found to be present in solution. Tetrahydrofuran solutions of 1-(⁶Li)-[1-¹³C]-2-phenylethyne in the presence or absence of N,N,N′,N′-tetramethylpolymethylenediamines show a pentuplett ¹³C-NMR signal [δ=140 ppm, J(C,Li)=8.2 Hz] from the labelled C-atom at low temperatures (?95 to ?110°). This proves the dimeric structure. When (⁶Li)BuLi is added, a mixed dimer [(C₆H₅C?CLi)(C₄H₉Li)] is formed [δ=142 ppm, J(C,Li) = 7.8 Hz]. This is converted to a mixed tetramer [(C₆H₅C?CLi)(C₄H₉Li)₃] upon addition of larger amounts of (⁶Li)BuLi, as concluded from a signal at δ = 133.5 ppm, J(C,Li) = 5.6 Hz. The multiplicity of this signal suggests that a static tetramer is present, in which the C-atoms couple only with three next Li-neighbors.     

Structure Determination of an AgI‐Mediated Cytosine–Cytosine Base Pair within DNA Duplex in Solution with 1H/15N/109Ag NMR Spectroscopy

The structure of an Ag^I‐mediated cytosine–cytosine base pair, C–Ag^I–C, was determined with NMR spectroscopy in solution. The observation of 1‐bond ¹⁵N‐¹⁰⁹Ag J‐coupling (¹J(¹⁵N,¹⁰⁹Ag): 83 and 84 Hz) recorded within the C–Ag^I–C base pair evidenced the N3–Ag^I–N3 linkage in C–Ag^I–C. The triplet resonances of the N4 atoms in C–Ag^I–C demonstrated that each exocyclic N4 atom exists as an amino group (?NH₂), and any isomerization and/or N4–Ag^I bonding can be excluded. The 3D structure of Ag^I–DNA complex determined with NOEs was classified as a B‐form conformation with a notable propeller twist of C–Ag^I–C (?18.3±3.0°). The ¹⁰⁹Ag NMR chemical shift of C‐Ag^I‐C was recorded for cytidine/Ag^I complex (δ(¹⁰⁹Ag): 442 ppm) to completed full NMR characterization of the metal linkage. The structural interpretation of NMR data with quantum mechanical calculations corroborated the structure of the C–Ag^I–C base pair.