The phosphorus-31 and metal nuclear magnetic resonance spectra of complexes of tin(II) and lead(II) with tricyclohexylphosphine oxide, sulfide, and selenide

1982 ◽  
Vol 60 (23) ◽  
pp. 2921-2926 ◽  
Author(s):  
Philip A. W. Dean
Keyword(s):  
High Field ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Temperature Gradients ◽  
Large Temperature ◽  
Linear Variation ◽  
Small Temperature ◽  
Nuclear Magnetic Resonance Spectra ◽  
Small Temperature Variation ◽  
Reduced Temperature

The new stannous and plumbous complexes M(OP(C6H11)3)n2+ (n = 2 or 3, M = Sn or Pb) and [M(SP(C6H11)3)x(SeP-(C6H11)3)3−x]2+ (M = Sn or Pb) have been prepared in SO2 solution and characterized by their reduced temperature slow-exchange 31P and metal (119Sn or 207Pb) nmr spectra. No evidence could be found for complexes in which both OP(C6H11)3 and EP(C6H11)3 (E = S or Se) are coordinated to tin(II) or lead(II). The same pattern of chemical shifts is found in the 119Sn and 207Pb nmr spectra: δM(M(OP(C6H11)3)22+) < δM(M(OP(C6H11)3)32+ < δM(M(SP(C6H11)3)32+) < δM(M(SeP(C6H11)3)32+) and a monotonic but non-linear variation of δM with x for [M(SP(C6H11)3)x(SeP(C6H11)3)3−x]2+. From M(AsF6)2 in SO2 as reference, the range of the metal chemical shifts is 999–2079 ppm and 2407–7707 ppm in the 119Sn and 207Pb nmr spectra respectively. In the 31P nmr spectra, all of the appropriate two-bond M—P couplings are observed, but the fine structure expected from coupling to 31P could not always be observed in those metal nmr spectra which were measured at high field; it is suggested that these metal nmr spectra are "smeared out" by a combination of large temperature sensitivity of the metal chemical shifts and the small temperature variation allowed by the nmr spectrometer temperature controller and/or diffusion along any temperature gradients present along the length of the nmr sample.

The High Resolution NMR Spectra of Pesticides. II. The DDT-Type Compounds

1969 ◽  
Vol 52 (5) ◽  
pp. 1074-1092 ◽  
Author(s):  
L H Keith ◽  
A L Alford ◽  
A W Garrison
Keyword(s):  
Nuclear Magnetic Resonance ◽  
High Resolution ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Aromatic Rings ◽  
Nuclear Magnetic Resonance Spectra ◽  
High Resolution Nmr ◽  
Related Compounds ◽  
Deshielding Effect

Abstract The high resolution nuclear magnetic resonance spectra of the DDT class of pesticides and related compounds are discussed, including a study of the resonances of the aromatic protons as they are affected by various substiluents. The CCl3 moiety on the α-carbon strongly deshields the ortho protons on the aromatic rings, and this deshielding effect is greatly enhanced by substitution of a chlorine ortho rather than para on the aromatic ring. These deshielding effects are explained by a consideration of the electronegativity of the substituents and the stereochemistry of the molecule. The chemical shifts and coupling constants are tabulated.

The metal nuclear magnetic resonance spectra of some tin(II) and lead(II) complexes with polydentate phosphines

1983 ◽  
Vol 61 (8) ◽  
pp. 1795-1799 ◽  
Author(s):  
Philip A. W. Dean
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Narrow Range ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Spectra ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The previously reported 1:1 complexes formed in MeNO2, between M(SbF6)2 (M = Sn or Pb) and Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, P[(CH2)2PPh2]3, and [Formula: see text] have been studied by metal (119Sn or 207Pb) nmr. The metal chemical shifts span the comparatively narrow range of −586 to −792 ppm and 60 to −269 ppm, relative to the resonance of MMe4, for 119Sn and 207Pb nmr, respectively. The implications of these data regarding the denticity of the ligand in M(P[(CH2)2PPh2]3)2+ are discussed, and a comparison with the metal nmr spectra of related stannous and plumbous complexes is made.

The High Resolution NMR Spectra of Pesticides. III. The Carbamates

1970 ◽  
Vol 53 (1) ◽  
pp. 157-179 ◽  
Author(s):  
L H Keith ◽  
A L Alford
Keyword(s):  
Nuclear Magnetic Resonance ◽  
High Resolution ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Hindered Rotation ◽  
Solvent Dependence ◽  
Nuclear Magnetic Resonance Spectra ◽  
High Resolution Nmr ◽  
Proton Resonances

Abstract The high resolution nuclear magnetic resonance spectra of 35 carbamate pesticides and a major metabolite of one pesticide are discussed. The chemical shifts and coupling constants are tabulated and reproductions of the more complex or unusual spectra are included. A concentration and solvent dependence of both the NH-proton and the NCH3-proton resonances of an N-monosubstituted carbamate is discussed. Hindered rotation is observed in the N,N-dimethylcarbamates, the thiolcarbamates and the dithiocarbamates, but not in the N-methylcarbamates.

13C-NMR-Spektroskopie an polycyclischen Aromaten, IIΙ Die 13C-NMR-Spektren von Amino- und Dimethylaminonaphthalinen /13C NMR Spectroscopy of Polycyclic Aromatics, III The 13C NMR Spectra of Amino- and Dimethylaminonaphthalenes

1975 ◽  
Vol 30 (9-10) ◽  
pp. 794-799 ◽  
Author(s):  
Ludger Ernst
Keyword(s):  
13C Nmr ◽  
High Field ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Double Resonance ◽  
Substituent Effects ◽  
13C Nmr Spectroscopy ◽  
Polycyclic Aromatics ◽  
Electrophilic Reagents ◽  
C Nmr

The 13C NMR spectra of twelve amino-, dimethylamino-, diamino-, and bis(dimethylamino)naphthalenes are completely assigned by selective 13C{1H} double resonance and by interpretation of proton-coupled spectra. Strong substituent effects (Δδ) upon chemical shifts are observed and can largely be accounted for by mesomerism. The pronounced high-field shifts of C-6 in the 2-amino- and 2-dimethylaminonaphthalenes coincide with the enhanced reactivity of this position towards electrophilic reagents. In 1-dimethylaminonaphthalene and even more so in 1-dimethylamino-2-methylnaphthalene, conjugation is inhibited for steric reasons and Δδ’s are greatly diminished, thus giving an estimate for the contribution of resonance to substituent-induced shifts in the unhindered compounds. In two 1,8-disubstituted naphthalenes there are large deviations from additivity of substituent effects.

scholarly journals Carbon-13 nuclear magnetic resonance spectra of oxazoles

1979 ◽  
Vol 57 (23) ◽  
pp. 3168-3170 ◽  
Author(s):  
Henk Hiemstra ◽  
Hendrik A. Houwing ◽  
Okko Possel ◽  
Albert M. van Leusen
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Proton Coupling ◽  
Nuclear Magnetic Resonance Spectra ◽  
C Nmr ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The 13C nmr spectra of oxazole and eight mono- and disubstituted derivatives have been analyzed with regard to the chemical shifts and the various carbon–proton coupling constants of the ring carbons. The data of the parent oxazole are compared with thiazole and 1-methylimidazole.

A multinuclear (1H, 31P, 199Hg) nuclear magnetic resonance study of some complexes of mercury(II) with ditertiary phosphines

1985 ◽  
Vol 63 (11) ◽  
pp. 2829-2839 ◽  
Author(s):  
Philip A. W. Dean ◽  
Radhey S. Srivastava
Keyword(s):  
Spectral Properties ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Mixed Ligand Complex ◽  
Nuclear Magnetic Resonance Study ◽  
Chelate Complexes ◽  
Ligand Complex ◽  
The One ◽  
Reduced Temperature ◽  
Chelate Ring Size

From Hg(SbF6)2 and an appropriate amount of the ligands Ph2PCHRPPh2 (R = H or Me), 2:2, 1:2, and 1:3 M:L complexes have been prepared in MeNO2 solution and characterized by 1H, 31P, and 199Hg nmr spectroscopy. The 2:2 complexes are ligand-bridged, as are [Hg(Ph2PCH2PPh2)(Ph2PCHMePPh2)Hg]4+ and [Hg(Ph2PCH2PPh2)2Ag]3+ (prepared from Hg(SbF6)2, Ag(AsF6), or Ag(SbF6) and the ligand), examined by nmr for comparison. The complex [Hg(μ-Ph2PCHMePPh2)2Hg]4+ exists as two isomers, which interconvert slowly on the preparative timescale. The 1:2 complexes, and the analogous mixed ligand complex are shown by their nmr spectral properties to be examples of tetrahedral bis(chelate) complexes, which are very unusual for the Ph2PCHRPPh2 ligands. In the 1:3 complexes, and the one of the two possible mixed complexes identified, both η1-and η2-ligands appear to be present and these undergo rapid intramolecular η1-to-η2 exchange. The η1-bonding mode of Ph2PCH2PPh2 also occurs in [(η-Ph2P(CH2)2PPh2)Hg(η1-Ph2PCH2PPh2)2]2+ and [Hg(η1-Ph2PCH2PPh2)4]2+ as evidenced by their reduced temperature 31P nmr spectra in Me2CO—MeNO2.The complex [Hg(η2-Ph2PCH2PPh2)2]2+ has 31P and 199Hg nmr spectral properties significantly different from those of its acyclic analog [Hg(PMePh2)4]2+. To place this anomaly in perspective, the 31P and 199Hg nmr spectra of a much wider series of new bis(chelate) complexes [Hg(LL)(L′L′)]2+ have been obtained, with the ligand combinations LL = L′L′ = Ph2PNPhPPh2; LL = dppm, L′L′ = Ph2PNPhPPh2; LL = L′L′ = Ph2P(CH2)nPPh2(n = 2–4); LL = Ph2P(CH2)mPPh2, L′L′ = Ph2P(CH2)nPPh2 (m ≠ n; m = 1–3, n = 1–5). From the data for the last two series, it is found that only the bis(chelate) complex of Ph2PCH2PPh2 shows a large anomaly in its 199Hg chemical shift (anomalously high shielding), and that in [Hg(LL)(L′L′)]2+ values of 2J(PP), 1J(HgP), and 31P chemical shifts vary systematically with the ligand combination; of particular note, 1J(HgP) to LL decreases as the chelate ring size of L′L′ increases. These observations are discussed in terms of the variation in the intra-and inter-chelate PHgP angles expected in the complexes.

Phosphorus-31 nuclear magnetic resonance spectra of methylplatinum(II) and methylpalladium(II) cations containing 4-substituted pyridine ligands

1979 ◽  
Vol 57 (9) ◽  
pp. 958-960 ◽  
Author(s):  
Howard C. Clark ◽  
Charles R. Milne
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Lone Pair ◽  
Coupling Constants ◽  
The Other ◽  
Pyridine Ligands ◽  
Trans Influence ◽  
Nuclear Magnetic Resonance Spectra

The 31P nmr spectra of the compounds cis-[M(CH3)(L)diphos]PF6, where M = Pd, Pt; L = 4-C5H4NX; X = CH3, H, NMe2, COOMe, COMe, CN; diphos = 1,2-bisdiphenylphosphino ethane, have been recorded. The 31P chemical shifts and 31P–195Pt coupling constants decrease regularly as the ρ values of the substituent on pyridine decrease. These trends are attributed to decreasing lone pair donation from phosphorus as the electron donating ability of the other ligands on the metal increases. The trans influence of the coordinated pyridine molecule, as measured by J(195Pt–31P), is greater than its cis influence on the phosphorus atoms.

scholarly journals Zero-Field Nuclear Magnetic Resonance of Chemically Exchanging Systems

2019 ◽  
Author(s):  
Danila Barskiy ◽  
Michael C. D. Tayler ◽  
Irene Marco-Rius ◽  
John Kurhanewicz ◽  
Daniel B. Vigneron ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
High Field ◽  
Nmr Spectra ◽  
Chemical Exchange ◽  
Chemical Shifts ◽  
Proton Exchange ◽  
Zero Field ◽  
Resonance Frequencies ◽  
Nuclear Magnetic

Zero- and ultralow-field (ZULF) nuclear magnetic resonance (NMR) is an emerging tool for precision chemical analysis. Unlike conventional (high-field) NMR, which relies on chemical shifts for molecular identification, zero-field analog reports <i>J</i>-spectra that depend on the nuclear spin-spin coupling topology of molecules under investigation. While chemical shifts are usually a small fraction of the resonance frequencies, <i>J</i>-spectra for various spin systems are completely different from each other. In this work, we use zero-field NMR to study dynamic chemical processes and investigate the influence of chemical exchange on ZULF NMR spectra. We develop a computation approach that allows quantitative calculation of ZULF NMR spectra in the presence of chemical exchange and apply it to study aqueous solutions of [<sup>15</sup>N]ammonium as a model system. In this system, proton exchange rates span more than three orders of magnitude depending on acidity (pH), as monitored by high-field and ZULF NMR. We show that chemical exchange substantially affects the <i>J</i>-coupled NMR spectra and, in some cases, can lead to degradation and complete disappearance of the spectral features. To demonstrate potential applications of ZULF NMR for chemistry and biomedicine, we show a ZULF NMR spectrum of [2-<sup>13</sup>C]pyruvic acid hyperpolarized via dissolution dynamic nuclear polarization (dDNP). The metabolism of pyruvate provides valuable biochemical information and its monitoring by zero-field NMR could give spectral resolution that is hard to achieve at high magnetic fields. We foresee applications of affordable and scalable ZULF NMR coupled with hyperpolarization modalities to study chemical exchange phenomena in vivo and in situations where high-field NMR detection is not possible to implement.<br>

Carbon-13 nuclear magnetic resonance spectra of E-silyl-alkenes

1980 ◽  
Vol 58 (4) ◽  
pp. 361-368 ◽  
Author(s):  
Constantinos A. Tsipis ◽  
Constantinos A. Tsoleridis
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Quantitative Analysis ◽  
Nmr Spectroscopy ◽  
Carbon Atom ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
H Nmr ◽  
Nuclear Magnetic Resonance Spectra ◽  
C Nmr

Carbon-13 nmr chemical shifts of a number of E-silyl-alkenes containing the silyl substituent at an sp2 carbon atom are presented. Assignments of the chemical shifts have been made by noting systematic variations in the spectra with changes in substituents and by comparison of the chemical shifts to those of the corresponding unsubstituted alkenes. The substituent effects observed were explained on the basis of the π-acceptor ability of the silyl substituents and the structure of the molecules. Comparing the 13C nmr spectra of the E-silyl-alkenes and those of the corresponding unsubstituted alkenes, differential chemical shifts have been obtained which can be used as empirical substituent parameters for the prediction of the 13C nmr spectra of other E-silyl-alkenes not yet studied. It was also demonstrated that 13C nmr spectroscopy can be used without resorting to special techniques (gated decoupling and the addition of paramagnetics) as an alternative method to the 1H nmr for the quantitative analysis of mixtures of regio-isomer E-silyl-alkenes.

A 31P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the 31P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

1981 ◽  
Vol 59 (1) ◽  
pp. 50-61 ◽  
Author(s):  
Philip A. W. Dean ◽  
Donald D. Phillips ◽  
Lijana Polensek
Keyword(s):  
Nmr Spectra ◽  
31P Nmr ◽  
Coupling Constants ◽  
Phosphine Oxides ◽  
Polydentate Ligands ◽  
Intramolecular Exchange ◽  
Nuclear Magnetic Resonance Spectra ◽  
Reduced Temperature

31P nmr has been used to show that, in MeNO2, M(SbF6)2 (M = Sn or Pb) forms 1:1 complexes with Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, [Formula: see text][Formula: see text]P[(CH2)2PPh2]3, and Ph2P[(CH2)2PPh]2(CH2)2PPh2. The phosphonium ligands are formed in situ. Spectra characteristics of slow inter- and intramolecular exchange were obtained in all cases except, perhaps, those involving the last two ligands, which may be involved in rapid intramolecular exchange. For the first five ligands, the maximum denticity is achieved and unambiguous one-bond M(II)—31P (M = 117/119Sn or 207Pb) coupling constants are reported and discussed. In the presence of M(SbF6)2 (M = Sn or Pb). PPh3 is protonated in MeNO2, while in acetone Sn(SbF6)2 forms a 1:1 complex with PPh3 which appears to be solvent-inserted, [Sn—O—CMe2PPh3]2+.Reduced temperature 31P nmr spectroscopy has allowed the detection of 1:2 and 1:3 (M:L) complexes of OPPh3, and 1:1 complexes of Ph2P(O)(CH2)2P(O)Ph2, PhP(O)[(CH2)2P(O)Ph2]2, and (O)P[(CH2)2P(O)Ph2]3, with both tin(II) and lead(II). The 1:1 complexes with polydentate ligands are isolable; nmr shows that the maximum denticity occurs except with the last ligand which behaves in a tridentate manner. Several two-bond M—O—P coupling constants have been obtained. Also, the changes which complexation produces in the P—P couplings are compared with changes produced in the analogous phosphine complexes.The synthesis and characterization of Ph2P(E)[(CH2)2P(E)Ph]2(CH2)2P(E)Ph2 (E = S or Se) and (Se)P[(CH2)2P(Se)Ph2]3 are reported. The 31P nmr spectra of these compounds are compared with those of the parent tetraphosphines and other members of the corresponding tetraoxide–tetrachalcogenide series.

Sign in / Sign up

Export Citation Format

Share Document