NMR-spektroskopische Untersuchungen an 15N-markierten N-Methyl-imidodiphosphorsäure-Derivaten

NMR Spectroscopic Studies of ¹⁵N Labelled N-Methyl-imidodiphosphoric Acid Derivatives ¹⁵N labelled compounds (EtO)_mCl_2?m(O)P? NMe? P(O)(OEt)_nCl_2?n (m = 0–2, n = 0–2) were prepared as a mixture and investigated by means of ³¹P and ¹⁵N NMR spectroscopy. The chemical shift values δ_P and δ_N, and the coupling constants ¹J_PN and ²J_PP are discussed and interpreted qualitatively by semiempirical quantumchemical calculations (CNDO/2) using POPLE 'S ΔE-model.     

NMR-spektroskopische Untersuchungen an Mercaptophosphazenen. I. Verlauf der Reaktion von Natriumethylmercaptid mit Hexachlorocyclotriphosphazatrien bzw. Octachlorocyclotetraphosphazatetraen

N.M.R. Spectroscopic Investigations of Thiophosphazenes. I. Reactions of Sodium Ethylthiolate with Hexachlorocyclotriphosphazatriene and Octachlorocyclotetraphosphazatetraene By reactions of hexachlorocyclotriphosphazatriene with an excess of sodium ethylthiolate as a suspension in ether all of the possible geminal derivatives N₃P₃Cl_6?n(SEt)_n; n = 1–6, are formed in different quantities. Products from reactions of octachlorocyclotetraphosphazatetraene with sodium ethylthiolate, N₄P₄Cl_8?n(SEt)_n, likewise contain all of the geminally substituted derivatives up to n = 8 with the exception of the derivatives with n = 1 and n = 7. Compounds with n = 3, 4, or 5 exist in two geminal isomers respectively. Nongeminal ethylthiochlorophosphazenes were not found by any reaction. The formed compounds were isolated by chromatographic methods and studied by ³¹P n.m.r. spectroscopy.     

NMR-spektroskopische Untersuchungen an 15N-markierten geminal disubstituierten Cyclotriphosphazenen

NMR Spectroscopic Studies of ¹⁵N Labelled Geminally Disubstituted Cyclotriphosphazenes It is demonstrated by means of some selected ¹⁵N labelled geminally disubstituted cyclotriphosphazenes, ¹⁵N₃P₃X₄Y₂ (X = Cl; Y = F, NH₂, or SEt), as an example, that the coupling constants ¹J_PN may be of different signs. The absolute value of ¹J_PN is significantly influenced only by those substituents, which are bonded to the phosphorus nucleus directly concerned in the coupling. Also the ¹⁵N chemical shifts are only changed by substituents on directly bonded phosphorus atoms.     

NMR-spektroskopische Untersuchungen an 15N-markierten Phenylamidochlorocyclotetraphosphazenen

NMR Spectroscopic Studies of ¹⁵N Labelled Phenylamidochlorocyclotetraphosphazenes Some endocyclically ¹⁵N labelled phenylamidochlorocyclotetraphosphazenes, ¹⁵N₄P₄Cl₇NHPh, 6,8-¹⁵N₄P₄Cl₆(NHPh)₂ and 4,8-¹⁵N₄P₄Cl₆(NHPh)₂, as well as the corresponding exocyclically ¹⁵N labelled compounds N₄P₄Cl₇¹⁵NHPh, 6,8-N₄P₄Cl₆(¹⁵NHPh)₂ and 4,8-N₄P₄Cl₆(¹⁵NHPh)₂ were prepared, and the ³¹P and ¹⁵N NMR spectra were recorded. In the case of the endocyclically labelled compounds it is possible to determine the relative signs of the coupling constants ¹J_PN by means of spectra simulation. In order to interprete the relatively large coupling constants ³J_PN to the exocyclic nitrogen a Karplus diagram was calculated and discussed.     

NMR-spektroskopische Untersuchungen an 15N-markierten N-Phosphorylphosphazenen und Imidodiphosphorsäure-Derivaten

N.M.R. Spectroscopic Studies of ¹⁵N Labelled N-Phosphorylphosphazenes and Imidodiphosphoric Acid Derivatives ¹⁵N labelled compounds were prepared and investigated by means of ³¹P- and ¹⁵N-NMR spectroscopy. The chemical shift values δ_P and δ_N, and the coupling constants ¹J_PN and ²J_PP are discussed and interpreted qualitatively by semiempirical quantumchemical calculations (CNDO/2) using POPLE 'S ΔE-model.     

NMR-spektroskopische Untersuchungen zur Thiolyse von Decachlorocyclopentaphosphazen,N5P5Cl10

NMR Spectroscopic Studies on the Thiolysis Reaction of Decachlorocyclopentaphosphazenen, N₅P₅Cl₁₀ A series of different but exclusively geminally substituted products, N₅P₅Cl_10?n(SR)_n, is formed by reactions of decachlorocyclopentaphosphazene, N₅P₅Cl₁₀, with sodium ethanethiolate, NaSEt, or benzenethiolate, NaSPh, in benzene or ether. The degree of substitution is low (mainly up to n = 4); intensified conditions do not result in further substitution but in decomposition. The compounds were separated by column chromatography and identified by ³¹P NMR spectroscopy. ³¹P chemical shifts and P—P coupling constants of the investigated compounds systematically change with the progressive substitution by SR groups. The chlorine-replacement pattern is discussed.     

1H-, 13C-UND 31P-NMR-SPEKTROSKOPISCHE UNTERSUCHUNGEN AN BIS-(DIALKOXYTHIOPHOSPHORYL)-UND-(DIALKOXYPHOSPHORYL)-SULFANEN UND-POLYSULFANEN

Abstract

Compounds of the following structure

(R¹O)₂(X)P[sbnd]Y–P(X)(OR²)₂

(X = O, Y = S_n (n = 1–4), R¹ = R² = Me, iPr;

X = S, Y = S_n (n = 1–4), R¹, R² = Me, Et, iPr, iBu;

X = S, Y = S-Se-S, S-Te-S, R¹ = R² = Me

were prepared and their NMR spectra were analysed. Depending on the number of sulfur atoms, bonded between the phosphorus atoms, typical ranges of the P-P coupling constants were found for the different sulfanes investigated: ²J_PP from-10 to-20 Hz, ³J_PP less than 3 Hz, ⁴J_PP from +10 to +13 Hz and ⁵J_PP less than 1 Hz. For the small vicinal coupling constants and the relatively large values of ⁴J_PP different possibilities of their interpretation are given.     

Beiträge zur Chemie der Silicium–Stickstoff-Verbindungen. CXXX. Kernresonanz- und infrarotspektroskopische Untersuchungen an Methylaminosilanen

Chemistry of Silicon-Nitrogen Compounds. CXXX. N.M.R. and I.R. Spectroscopic Investigations on Methylaminosilanes The attachment of a silicon atom to methylamino groups leads in the pure compounds I to VII to a HNCH coupling constant for the protons of J = 6–7 Hz. A similar effect is also observed in solution, except in CH₂Cl₂ and CHCl₃. The correct assignment of the n.m.r. signals for IV is shown in Fig. 1. I to VII have practically the same basic properties as can be concluded from the invariable shift of the C? D stretching vibration of 35 cm^?1 for CDCl₃.     

IR- und NMR-spektroskopische Untersuchungen zu Substituenteneffekten in Siloxy- und Alkoxysilanen

I.R. and N.M.R. Spectroscopic Investigations on Substituent Effects in Siloxy and Alkoxysilanes Siloxy and alkoxysilanes of the types (RMe₂SiO)₃SiH, (RMe₂CO)₃SiH, (Me_3–nPh_nSiO)_m(Me₃SiO)_3–mSiH (m = 1—3, n = 1—3), and Me_3–n(RMe₂SiO)_nSiH (n = 1—3) have been prepared. The influence of the substituent effects through the (Me₂)Si? O- a (Me₂)C? O- group on the Si? H band is approximately equal.     

NMR-spektroskopische Untersuchungen an Fluoro-diaza-diphosphetidinen und Fluoro-λ5-monophosphazenen

N.M.R. Investigations of Fluorodiazadiphosphetidines and Fluoro-λ⁵-monophosphazenes The ¹⁹F and ³¹P n.m.r. data of 37 fluorodiazadiphosphetidines [RR′PF? NC₆H₄X]₂, and 62 fluoro-λ⁵-monophosphazenes, RR′PF=NC₆H₄X, are submitted. In the case of tetrafluorodiazadiphosphetidines, [RPF₂? NC₆H₄X]₂, an intramolecular exchange of the fluorine atoms at phosphorus has to be concluded from the n.m.r. data. The influence of the substituents R and X on the n.m.r. parameters is discussed using simple models of molecular structure.     

NMR-spektroskopische Untersuchungen an Undecamethylcyclohexasilanyl-Derivaten

The structure and ²⁹Si chemical shifts of nine undecamethylcyclohexasilanyl derivatives, Si₆Me₁₁X (X = Fe(CO)₂cp, SO₃CF₃, F, Cl, Br, I, H, C CH, OH), have been assigned using ¹J_SiSi and ²J_SiSi derived from ²⁹Si-INADEQUATE and ²⁹Si-INEPT-INADEQUATE and ²⁹Si-INEPT-INADEQUATE NMR spectra. Only the halo-derivatives exhibit linear correlation between ¹J_SiSi and Pauling electronegativities. The correlation of other derivatives is improved by employing Inamato's inductivity values. A new synthetic route to Si₆Me₁₁X (X = F, Cl, Br, I) has been developed.     

Spektroskopische Untersuchungen zu Substituenteneffekten in Silylmethylsilanen

Spectroscopic Investigations on Substituent Effects in Silylmethylsilanes The silanes Me_3?n(Me₃SiCH₂)_nSiH (n = 1–3), (RMe₂SiCH₂)₃SiH (R = n-Bu, n-Pr, Et, PhCH₂, Ph) and Me₃ElCH₂SiMe₂H (El = Ge, Sn) were prepared. The frequencies of the Si? H stretching vibration, the ²⁹Si? ¹H coupling constants and the ²⁹Si n.m.r. chemical shifts were measured. The ?(SiH) and J(²⁹Si? ¹H) values in the silanes Me_3?n(Me₃SiCH₂)_nSiH depend on the number of trimethylsilymethyl groups. There is hardly an influence of the substituents R on these values in the silanes (RMe₂SiCH₂)₃SiH. The frequencies of the Si? H stretching vibrations in the silanes Me₃ElCH₂SiMe₂H (El = Si, Ge, Sn) show the order Si?Ge > Sn. The ₂₉Si n.m.r. chemical shifts of the Si(H) signals are approximately equal in the silanes Me_3?n(Me₃SiCH₂)_nSiH and (RMe₂SiCH₂)₃SiH.     

N-Methyl-N-diäthoxyphosphorylamido-Derivate des Hexachlorocyclotriphosphazatriens. IV. NMR-spektroskopische Untersuchungen zur Konstitution der Ammonolyseprodukte von N-Methyl-N-diäthoxyphosphorylamido-chloro-cyclotriphosphazatrienen

N-Methyl-N-Diethoxyphosphorylamido Derivatives of Hexachlorocyclotriphosphazatriens. IV N.M.R. Spectroscopic Investigations of the Products of the Ammonolysis of N-methyl-N-diethoxyphosphorylamindo-chloro-cyclotriphosphazatrienes Broad band ¹H decoupled ³¹P n.m.r. spectra of products obtained by ammonolysis of N-methyl-N-diethoxyphosphorylamido-chloro-cyclotriphosphazatrienes provide essential hints at the constitution of these compounds. In this connection it may be easily demonstrated, both amino groups of N₃P₃Cl₃[NCH₃P(O)(OC₂H₅)₂][NH₂]₂ as well as of N₃P₃Cl₂[NCH₃P(O)(OC₂H₅)₂]₂ [NH₂]₂ are arranged geminally. The spectral parameters were found and verified by simulation of spectra. The simulated ³¹P spectra agree closely with the observed ones. The conclusions from the ³¹P n.m.r. spectra are complemented by these from the ¹H n.m.r. spectra.     

Synthese und NMR-spektroskopische Untersuchungen von Dibenzo[d,g]-1,3-dioxa-2-element-6-silocinen

Synthesis and NMR Spectroscopic Investigations of Dibenzo [d,g]-1,3-dioxa-2-element-6-silocine Bis-(o-halogenoaroxy)silanes react with sodium via metallation and a fast two-step [1.3]-rearrangement to the sodium salts of bis(o-hydroxyaryl)silanes. These are cyclized in a one-pot-reaction with element halides of silicon, phosphorus and arsenic to the title compounds of the general formula R¹R²Si(C₆H₄O)₂E (E = SiR₂, P(Y)R, As(Y)R). One conformer is prefered according to N.M.R. spectroscopical investigations.     

15N, 31P,and 13C NMR Spectroscopy of N-Arylsulfonyl-and N-Arylcarbonyl-P,P,P-triphenylphospha-λ-Azenes. Substituent Effects and Electronic Structure

Abstract

The ¹⁵N, ³¹P and ³¹C NMR spectra of several series of phospha-λ⁵-azenes are reported. For the N-arylsulfonyl-P,P,P-triphenylphospha-δ⁵-azene series (R-C₆H₄N-SO₂-PPh₃), the ³¹P chemical shifts, various ¹³C chemical shifts and ¹J_PN were observed to correlate linearly with the Hammett σ constants. Interestingly, the ¹⁵N chemical shifts did not correlate acceptably with any σ or with the Taft dual substituent parameter equation, and 1J_PC was invariant with substituent. For the N-arylcarbonyl-P,P,P-triphenylphospha-λ⁵-azene series (R-C₆H₄-CO-N=PPh₃), δ_31P and various δ_13C's were observed to linearly correlate with the δ constants, while δ_15N, ¹J_PN and ¹J_PC correlated with both the σ and σ constants. For the N-phenyl-P,P,P-triarylphospha-λ⁵-azene series [Ph-N=P(C₆H₄-R)₃] the best correlations were observed between ³¹P, ¹⁵N and several ¹³C chemical shifts and the σ constants.     

Infrarotspektroskopische Untersuchungen an matrixisoliertem Nitrosyljodid

Infrared Spectroscopic Investigations on Matrix Isolated Nitrosyliodide On vacuum-ultraviolett photolysis of HI/NO/Kr samples during condensation at 12 K various oxides of nitrogen are also obtained as HNO and INO. The infrared absorptions of INO are found to be ν₁ = 1 806 cm^?1, ν₂ = 468 cm^?1, the analogous fundamentals of ¹⁵N labelled INO are ν₁ = 1 775 cm^?1, ν₂ = 458 cm^?1.     

Spektroskopische Untersuchungen an Schwefelverbindungen. VII. 1H- und 13C-NMR-spektroskopische Untersuchungen an Alkansulfinsäurechloriden und Chloroschwefligsäurealkylestern

Spectroscopic Studies on Sulphur Compounds. VII. ¹H- and ¹³C-NMR Spectroscopic Investigations of Sulphinic Acid Chlorides and Chloro-sulphurous Acid Alkylesters The temperature dependent ¹H- and ¹³C-n.m.r. spectra of the sulphinic acid chlorides R—S(O)Cl and of the chloro-sulphurous acid alkylesters RO—S(O)Cl with R = CH₃CH₂- and (CH₃)₂CH- have been measured. The differing behaviour of both nuclei is discussed in terms of inversion at the chiral sulphur atom.     

The B–N Bond in Some Aminoboranes and an Iminoborane,Studied by 11B and 15N NMR Spectroscopy and DFT Methods

¹⁵N NMR spectra of several aminoboranes (Me₂B–NMe₂, Cl₂B–NMe₂, Br₂B–NMe₂, OCH₂CH₂OB–NMe₂), three N‐pyrrolylboranes, and an iminoborane (tBu–B≡N–tBu) was measured. The spin‐spin coupling constants ¹J(¹⁵N, ¹¹B) were resolved at elevated temperatures. In the case of the iminoborane at 105 °C, the coupling constant ¹J(¹⁴N,¹¹B) = 57 Hz could also be determined from the ¹¹B NMR spectrum [from ¹⁵N NMR ¹J(¹⁵N,¹¹B) = 81 Hz]. Generally, there is no correlation between the magnitude of ¹J(¹⁵N,¹¹B) and the bond length d_BN. The values ¹J(¹⁵N,¹¹B) indicate that changes in σ bonding affect their magnitude, and the nature of the lone pair of electrons at nitrogen is of great importance. The calculated NMR parameters of an adduct of the iminoborane with an N‐heterocyclic carbene, show that the bonding situation around the BN double bond in the adduct is comparable with imines.     

NMR-spektroskopische Untersuchungen an Derivaten des 2,4-Dichlorphenoxyessigsäurehydrazids

Summary Derivatives of 2,4-dichlorphenoxyacetyl-hydrazides were prepared by reaction of the hydrazides with different aldehydes. NMR-spectroscopic investigations of these compounds show the existence of rotamers resulting from a nitrogen-carbonyl bond rotation. Contrary to substituted dithiocarbacinic acid derivatives noE/Z-isomerism relative to the C=N double bond could be demonstrated. In order to prove the structures we utilized chemical shift differences in the¹H-,¹³C- and¹⁵N-NMR-spectra, NH and CH coupling constants and NOE-difference measurements. The barriers of rotation were determined by NMR-measurements at various temperatures and line shape analysis using the computer program D-NMR 3.

     

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.