Cyclische Schwefeldiimide des Siliciums. 15N-NMR-Spektroskopie und die Röntgenstrukturanalyse des Achtrings tBu2Si(NSN)2SitBu2 / Cyclic Sulfur Diimides of Silicon. 15N NMR Spectroscopy and the X-Ray Analysis of the Eight-Membered Ring tBu2Si(NSN)2SitBu2

1993 ◽  
Vol 48 (8) ◽  
pp. 1041-1050 ◽  
Author(s):  
Max Herberhold ◽  
Silke Gerstmann ◽  
Wolfgang Milius ◽  
Bernd Wrackmeyer
Keyword(s):  
Nmr Spectroscopy ◽  
Pulse Sequences ◽  
Ring System ◽  
Membered Ring ◽  
Coupling Constants ◽  
Primary Amines ◽  
15N Nmr ◽  
Monoclinic Space Group ◽  
Small Magnitude ◽  
X Ray

Various six-membered cyclic sulfur diimides (3a—f) were prepared by aminolysis of the bis(chloro-dimethylsilyl)sulfur diimide (2) using NH3 (a) and primary amines RNH2 [R = Me (b), Et (c), nPr (d), nBu (e), iPr (f)]. Except for R = H, non-cyclic intermediates, the Si-monoamino- (7) and Si,Si′-diamino derivatives of 2 (8), were detetected for all groups R, including R = tBu (g). The reaction between R2SiCl2 and the sulfur diimide anion K[(NSN)SiMe3] gave non-cyclic silanes (9,10) and the eight-membered rings of the type R2Si(NSN)2SiR2 [R = Me (4), tBu (5)] of which 5 was studied by X-ray analysis (monoclinic, space group P21/c; planar ring system) and solid-state 15N and 29Si CP/MAS NMR spectroscopy. The ten-membered ring system 6 was obtained from the reaction between 1,2-dichlorotetramethyldisilane and bis(trimethylstannyl)sulfur diimide. All compounds were studied by 1H,13C, 15N and 29Si NMR. The δ15N NMR data proved useful to distinguish between fluxional systems with fast E/Z—Z/E isomerization (non-cyclic compounds 8 and the ten-membered cycle 6). Hahn-Echo-extended (HEED) polarization transfer (INEPT) pulse sequences served to measure coupling constants 1J(29Si15Namine) for the compounds 3 and 8. This also proved that the magnitude of 1J(29Si15NNSN) must be small (< 1 Hz). In the case of the compounds 3, the rather small magnitude of both 1J(29Si15Namine) and 1J(15N1H) (3a) indicated that the aminonitrogen atom adopts a pyramidal environment.

Application of Reverse Two-Dimensional 1H{15N} NMR Spectroscopy to the Characterization of Two Inorganic Compounds:

1987 ◽  
Vol 42 (6) ◽  
pp. 703-706 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Klaus Schamel ◽  
Karlheinz Guldner ◽  
Max Herberhold
Keyword(s):  
Nmr Spectroscopy ◽  
Chemical Shifts ◽  
Inorganic Compounds ◽  
Ring System ◽  
Coupling Constants ◽  
15N Nmr ◽  
Two Dimensional ◽  
Hydrogen Atoms ◽  
15N Nmr Spectroscopy

AbstractThe inorganic ring system linked to the [Cr(CO)5] fragment [R = tBu (1), NH2 (2)], has been studied by reverse two-dimensional, 2D, 1H{15N} NMR spectroscopy. In solution, the exchange of the N-H hydrogen atoms is slow on the NMR time scale. Chemical shifts δ(1H), δ(13C), δ(31P), δ(15N) and coupling constants 1J(31P1H), 2J(31P13C), 1J(31P15N) are reported. In the case of 2, the reduced coupling constants 2K(31PN1H) and 1K(31P15N) have the same sign.

Preparation and nuclear magnetic resonance characterization of N-bonded complexes of platinum(II) with phosphorus-nitrogen rings containing three-coordinate chalcogens: X-ray structure of [PtCl2(PEt3)]2(Ph4P2N4Se2Et2)

1993 ◽  
Vol 71 (11) ◽  
pp. 1821-1827 ◽  
Author(s):  
Tristram Chivers ◽  
Daniel D. Doxsee ◽  
Robert W. Hilts ◽  
Masood Parvez
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Nmr Spectroscopy ◽  
Magnetic Resonance ◽  
Nitrogen Atom ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
Hydrogen Atoms ◽  
X Ray ◽  
X Ray Crystallography

The reaction of 1,5-Ph4P2N4S2Ph2 with [PtCl2CPEt3)]2 in chloroform at 60 °C produces the 1:1 adduct trans-PtCl2(PEt3)(Ph4P2N4S2Ph2) in which the platinum is attached to a nitrogen atom on the basis of 31P nmr spectroscopy. By contrast, the corresponding reactions of 1,5-Ph4P2N4Se2R2 (R = Me, Et, Ph) produce the 2:1 adducts [PtCl2(PEt3)]2(Ph4P2N4Se2R2) (7a, R = Me; 7b, R = Et; 7c, R = Ph) which have been characterized by 1H, 31P and 77Se nmr spectroscopy and, in the case of 7b, by X-ray crystallography. Crystals of 7b are monoclinic, space group C2/c, with a = 27.803(7) Å, b = 12.378(7) Å, c = 15.752(8) Å, β = 115.49(2)°, V = 4893(3) Å3, and Z = 4. The least-squares refinement with anisotropic thermal parameters for all non-hydrogen atoms converged at R = 0.037 and Rw = 0.022. The platinum centres in 7b are attached to distal nitrogen atoms of the disordered P2N4Se2 ring. The reaction of the six-membered ring Ph4P2N3SPh with [PtCl2(PEt3)]2 in dichloromethane at 23 °C occurs in a regiospecific manner to give the 1:1 adduct PtCl2(PEt3)(Ph4P2N3SPh) in which, on the basis of 31P nmr spectroscopy, the platinum is coordinated to a nitrogen atom between phosphorus and sulfur.

Ten-Vertex Polyhedral Monocarbaborane Chemistry. The Novel High-Yield Formation of the Ten-Vertex closo Compound [6-(PMe2Ph)-closo-1-CB9H9] from the Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11]

1993 ◽  
Vol 58 (12) ◽  
pp. 2924-2935 ◽  
Author(s):  
Jane H. Jones ◽  
Bohumil Štíbr ◽  
John D. Kennedy ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
High Yield ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Yield Formation ◽  
Boiling Toluene

Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] in boiling toluene solution results in an elimination of the platinum centre and cluster closure to give the ten-vertex closo species [6-(PMe2Ph)-closo-1-CB9H9] in 85% yield as a colourles air stable solid. The product is characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystals (from hexane-dichloromethane) are monoclinic, space group P21/c, with a = 903.20(9), b = 1 481.86(11), c = 2 320.0(2) pm, β = 97.860(7)° and Z = 8, and the structure has been refined to R(Rw) = 0.045(0.051) for 3 281 observed reflections with Fo > 2.0σ(Fo). The clean high-yield elimination of a metal centre from a polyhedral metallaborane or metallaheteroborane species is very rare.

scholarly journals Homopiperazine (Hexahydro-1,4-diazepine)

Molbank ◽  
10.3390/m1200 ◽  
2021 ◽  
Vol 2021 (2) ◽  
pp. M1200
Author(s):  
R. Alan Aitken ◽  
Dheirya K. Sonecha ◽  
Alexandra M. Z. Slawin
Keyword(s):  
13C Nmr ◽  
Title Compound ◽  
Coupling Constants ◽  
15N Nmr ◽  
Time Data ◽  
Nmr Spectrum ◽  
X Ray ◽  
First Time

The X-ray structure of the title compound has been determined for the first time. Data on its 1H–13C-NMR coupling constants and 15N-NMR spectrum are also given.

An Intramolecular Boron Nitrogen Lewis Acid Base Pair on a Rigid Naphthyl Backbone

2012 ◽  
Vol 67 (6) ◽  
pp. 589-593 ◽  
Author(s):  
Daniel Winkelhaus ◽  
Beate Neumann ◽  
Norbert W. Mitzel
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Lewis Acid ◽  
Elemental Analysis ◽  
Base Pair ◽  
Ring System ◽  
X Ray Diffraction ◽  
Acid Base ◽  
X Ray ◽  
Boron Nitrogen

The reaction of (C6F5)2BCl with 8-lithio-N,N-dimethyl-1-naphthylamine (1) afforded the fivemembered ring system 8-bis(pentafluorophenyl)boryl-N,N-dimethyl-1-naphthylamine (2) with an intramolecular dative B-N bond. The compound was characterised by elemental analysis, NMR spectroscopy and single-crystal X-ray diffraction.

Chemie polyfunktioneller Moleküle, 108 Tetraedrische Kupfer(I)-Chelatkomplexe der Liganden Bis(diphenylphosphino)amin und Bis(diphenylphosphino)methan / Chemistry of Polyfunctional Molecules, 108 [1] Tetrahedral Copper(I) Chelate Complexes with the Ligands Bis(diphenylphosphino)amine and Bis(diphenylphosphino)methane

1991 ◽  
Vol 46 (12) ◽  
pp. 1699-1705 ◽  
Author(s):  
Jochen Ellermann ◽  
Falk A. Knoch ◽  
Klaus J. Meier
Keyword(s):  
Membered Ring ◽  
Monoclinic Space Group ◽  
Direct Reaction ◽  
Conductivity Data ◽  
Chelate Complexes ◽  
X Ray ◽  
Lattice Constants ◽  
H Nmr ◽  
Highly Strained ◽  
Nitrate Anions

Reaction of [Cu(PPh3)2(NO3)] (1) in acetone with bis(diphenylphosphino)amine (dppa, 2) yields [Cu(dppa)(PPh3)2]+NO3- (3a). [Cu(dppa)(PPh3)2]+PF6- (3b) has been synthesized by metatheses of 3a with NH4PF6. The salt [Cu(dppm)(PPh3)2]+PF6- (5b) has been prepared by an one batch reaction of [Cu(PPh3)2(NO3)] (1), bis(diphenylphosphino)methane (dppm, 4) and NH4PF6 in methanol, because [Cu(dppm)(PPh3)2]+NO3- (5a) could not be isolated by the direct reaction of 1 with 4. The IR, Raman, 31P{1H} NMR, 1H{31Ρ} NMR as well as the conductivity data are reported and discussed together with the X-ray crystal structure of 3a · 1.8 (CH3)2CO. The structure consists of copper atoms coordinated tetrahedrally by two PPh3 ligands and the chelating dppa ligand and features a highly strained four-membered ring. The distorted tetrahedral cations are hydrogen bridged to the nitrate anions. The colourless needles of 3a· 1.8 (CH3)2CO crystallize in the monoclinic space group C 2/c, with the lattice constants a = 4189.2(27); b = 1223.7(8); c = 2717.8(15) pm;β = 113.16(4)°.

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.

scholarly journals New Spiro-Tin Compounds: Reaction of N,N′-Dialkyl Sulfur Diimides with Cyclic Bis(amino)stannylenes - Unexpected Formation of a N-N Bond

1995 ◽  
Vol 50 (12) ◽  
pp. 1811-1817 ◽  
Author(s):  
Max Herberhold ◽  
Christian Köhler ◽  
Wolfgang Milius ◽  
Bernd Wrackmeyer
Keyword(s):  
Molecular Structure ◽  
Magnetic Resonance ◽  
Single Crystal ◽  
Structure Analysis ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
Unexpected Formation ◽  
Tin Compounds ◽  
X Ray ◽  
Tert Butyl

N,N′-Dialkyl sulfur diimides (1), R(NSN)R [R = Me (a), Et (b), nPr (c), nBu (d)] react with cyclic bis(amino)stannylenes such as 1,3-di-tert-butyl-4,4-dimethyl-1,3,4,2λ2-diazasilastannetedine (2) or 1,3-di-tert-butyl-4,4,5,5-tetramethyl-1,3,4,5,2λ2-diazadisilastannolidine (3) in a 2:1 ratio to give the new spiro-tin(IV) compounds 5a-d, 6b and 6c, built from the respective cyclic bis(amino)stannylene and a seven-membered ring in which the two sulfur diimide groups are coupled via a N-N bond and across the tin atom. A 1:1 adduct 4 is proposed as an intermediate which is the final product 4e in the case of R = tBu (1e). The products were characterized by multinuclear magnetic resonance (1H, 13C, 15N, 29Si, 119Sn NMR), and in the case of 5c the molecular structure was determined by single crystal X-ray structure analysis [monoclinic, space group C2/c ; a = 1504.1(3), b = 1393.3(3), c = 1688.6(3) pm; β = 115.71(3)°].

Zur Darstellung und Struktur des 1.3-Dichloro-5-N.N-dimethylamino-1.3-dithia-2.4.6-triazins / Synthesis and Structure of 1,3-Dichloro-5-N,N-dimethylamino-1,3-dithia-2,4,6-triazine

1983 ◽  
Vol 38 (3) ◽  
pp. 347-349 ◽  
Author(s):  
Herbert W. Roesky ◽  
Pierre Schäfer ◽  
Mathias Noltemeyer ◽  
George M. Sheldrick
Keyword(s):  
Structure Analysis ◽  
Nmr Spectra ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cl Atoms ◽  
C Nmr

Abstract The six membered ring of composition (CH3)2NCN3S2Cl2 3 a was prepared from N,N-dimethylguanidinhydrochloride and trithiadiazindichloride. 3 a was characterized on the basis of mass, 1H, 13C NMR spectra and X-ray structure analysis. Crystals of 3 a are monoclinic, space group P21/c, with a = 660.3(6), b = 834.5(7), c = 1774.7(15) pm, β = 112.83(6)° and Z = 4. The C2N unit lies approximately in the plane of the [-CNSNSN-] ring, with both Cl atoms on the same side of the ring.

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