Umwandlung von η2-Thiocarbenkomplexen des Molybdäns und Wolframs in Metalla-thia-cyclopropan-Systeme / Conversion of η2-Thiocarbene Complexes of Molybdenum and Tungsten to Metalla-thio-cyclopropane Systems

1995 ◽  
Vol 50 (12) ◽  
pp. 1839-1844
Author(s):  
C. Ogric ◽  
W. Schütt ◽  
T. Lehotkay ◽  
E. Herdtweck ◽  
F. R. Kreißl
Keyword(s):  
Crystal Structure ◽  
Carbon Atom ◽  
Sodium Azide ◽  
Mass Spectra ◽  
Sodium Thiosulfate ◽  
Substitution Reactions ◽  
Space Group ◽  
And Tungsten

Cationic η2-thiocarbene complexes of molybdenum and tungsten [Cp(CO)2Me][ BF4] (M = Mo, W; R = Ph, Tol; L = CO, PMe3) react with the germylene Ge{N(tBu)CH2CH2N(tBu)}, the plumbylene Pb{N(SiMe3)2}2, or with sodium azide and sodium thiosulfate to give neutral metalla-thia-cyclopropane complexes Cp(CO)2-. Instead of the expected cycloaddition or substitution reactions the formal addition of thiomethanolat at the carbene carbon atom is observed. On treating the corresponding trimethylphosphine substituted η2-thiocarbene complex of molybdenum [Cp(CO)(PMe3)[BF4] with diethylamine or N,N,N′,N′-tetramethylguanidine a cationic molybda-thia-cyclopropane system is formed. The products have been characterized by 1H, 13C, 31P NMR, IR and mass spectra. The crystal structure of 5a has been determined; space group with a = 1340,4(2), b - 1097,7(1), c = 1101,8(5) pm and Z = 4.

Zur Cycloaddition von Azidoameisensäuremethylester an die Metall-Carben-Doppelbindung in η2-Thiocarbenkomplexen des Molybdäns und Wolframs / Cycloaddition of Azidoformic Acid Methylester to the Metal Carbon Double Bond of η2-Thiocarbene Complexes of Molybdenum and Tungsten

1993 ◽  
Vol 48 (11) ◽  
pp. 1481-1487
Author(s):  
Fritz R. Kreißl ◽  
Wolfgang Schutt ◽  
Josef Ostermeier ◽  
Claudia M. Stegmair ◽  
Waltraud Ullrich ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Double Bond ◽  
Mass Spectra ◽  
Space Group ◽  
Carbon Double Bond ◽  
Bicyclic System ◽  
And Tungsten

Cationic η2-thiocarbene complexes of molybdenum and tungsten [Cp(CO)PMe3[BF4] (R = Me, Ph, Tol) add N3COOMe to the electron rich metal carbon double bond to yield the corresponding bicyclic system. The products have been characterized by 1H, 13C, 31P NMR, IR and mass spectra. The crystal structure of 4b has been determined: space group P21/n with a = 1749.9(7), b = 827.9(1), c = 1846.8(7) pm and Z = 4.

Substitutionsreaktionen an der N-Chlornitrenogruppe des [WCl4(NCl)]2. Die Kristallstrukturen von [CH3CN—WCl4(NSMe)] und [WNCl3 · NC—CH3]4 / Substitution Reactions at the N-Chloronitreno Group of [WCl4(NCl)]2. The Crystal Structures of [CH3CN—WCl4(NSMe)] and [WNCl3 · NC—CH3]4

1989 ◽  
Vol 44 (8) ◽  
pp. 903-910 ◽  
Author(s):  
Astrid Görge ◽  
Ute Patt-Siebel ◽  
Ulrich Müller ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Ir Spectra ◽  
Structure Determination ◽  
Monoclinic Space Group ◽  
Trans Position ◽  
Crystal Data ◽  
Substitution Reactions ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

[WCl4(NCl)]2 reacts in acetonitrile with the trimethylsilyl compounds Me3SiSR (R = Me, Ph), and Me3SiESiMe3 (E = S, Se), with substitution of the chlorine atom of the N-chloronitreno group W=N–Cl and formation of CH3CN–WCl4(NSR) and CH3CN–WCl4(NEN)WCl4–NCCH3, respectively. Excess Me3SiBr reacts with CH3CN–WCl4(NSMe) to afford CH3CN–WBr4(NSMe). [CH3CN–WNCl3]4 was obtained from CH3CN–WCl4(NCl) and N(SiMe3)3. The products were characterized by their IR spectra. Two X-ray crystal structure determinations were also carried out. CH3CN—WCl4(NSMe) forms twinned crystals, and only non-overlapping reflexions of one of the twin individuals were used for the structure determination (846 unique values, R = 0.055). Crystal data: a = 592.4(2), b = 758.8(2), c = 1203.7(8) pm, β = 95.06(4)°, monoclinic, space group P21/m, Z = 2. The compound is a monomer in which the acetonitrile ligand is situated in the trans position to the W≡N–S̱̅–Me group. The bond lengths (W≡N 174(2), N–S 161(2) pm) and bond angles (WNS 176(1), NSC 102.1(9)°) are in agreement with the proposed formula. Crystal data for [CH3CN–WNCl3]4: a = 1009.5(2), b = 1274.5(2), c = 1287.9(2) pm, β = 108.17(1)°, monoclinic, space group P21/c, Z = 2 (2113 unique reflexions, R = 0.057). The compound forms tetrameric units, in which the W atoms form a square and are linked with one another via N atoms at alternating distances (W=N 171(2), W–N 207(2), W–NCMe 238(2) pm).

Ligand Substitution Reactions of the Nickel-Sulphur Cluster [Ni3(μ3-S)2(PEt3)6]2+. X-Ray Crystal Structure of [Ni3(μ3-S)2(PEt3)2(S2CNEt2)2]

1991 ◽  
Vol 46 (9) ◽  
pp. 1161-1164 ◽  
Author(s):  
Franco Cecconi ◽  
Carlo A. Ghilardi ◽  
Stefano Midollini ◽  
Annabella Orlandini
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Single Crystal ◽  
Inner Core ◽  
Ligand Substitution ◽  
Diphosphine Ligands ◽  
X Ray Diffraction ◽  
Substitution Reactions ◽  
Space Group ◽  
X Ray

Compounds of the type [Ni3S2(PR3)6]X2 (R = Me, Et; X = BPh4, ClO4) react with dithiocarbamate and diphosphine ligands to yield products [Ni3S2(PEt3)2(S2CNEt2)2] (1), [Ni3S2(PMe3)2(S2CNEt2)2] (2), and [Ni3S2(PMe3)2(dppe)2][BPh4]2 (3). The molecular structure of 1 has been established by single crystal X-ray diffraction. Space group C2/c, a = 25.137(3), b = 9.084(1), c = 18.333(2) Å, β = 123.41(2)°, Ζ = 4, 1128 observed unique reflections, R = 0.041. The inner core of 1 consists of a triangle of nickel atoms capped by two triply bridging sulphur ligands.

Synthesis and Structure of the Substituted Lithium Benzyl [Li(tmeda)2]+[C(PMe2)(SiMe3)C6H3-3,5-Me2]-. The First Metal Phosphinomethanide Consisting of Solvent-Separated Ion Pairs

2000 ◽  
Vol 55 (12) ◽  
pp. 1114-1120 ◽  
Author(s):  
Volker Knapp ◽  
Martin Winkler ◽  
Gerhard Müller
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Carbon Atom ◽  
Structure Data ◽  
Crystal Structure Data ◽  
Ion Pairs ◽  
Space Group ◽  
Bonding Parameters ◽  
Unique Data ◽  
Benzylic Carbon

The lithium dimethylphosphinomethanide with trimethylsilyl and 3,5-dimethylphenyl substituents in a position [Li(tmeda)2]+[C(PMe2)(SiMe3)C6H3−3 ,5-Me2]− (2) was synthesized from Me2P-CH(SiMe3)C6H3−3 ,5-Me2 (1) and LinnBu/tmeda in hexane in 56% yield (tmeda = N, N, N′, N′-tetramethylethylenediamine). In the solid state it consists of solvent-separated ion pairs which probably is also the case in solution (crystal structure data: tetragonal, space group I41cd, a = b = 19.303(3), c = 34.905(7) Å, Z = 16, R(F) = 0.054 for 2309 unique data and 299 refined parameters). The a-substituted lithium benzyl 2 is the first metal phosphinomethanide containing “free”, uncoordinated anions in the solid state. The lack of metal coordination of the anion is reflected in the bonding parameters at the planar carbanionoid benzylic carbon atom C1 (C1-P 1.773(8), C1-Si 1.846(8), C1-C2(Ph) 1.442(9) Å; C2-C1-P 125.3(5), C2-C1-Si 127.1(5), P-C1-Si 107.5(3)°; sum of the angles at C1: 359.9°).

Synthesis and structural study of aminals derived from 8-aminoquinoline and 1-aminonaphtalene

1987 ◽  
Vol 65 (4) ◽  
pp. 687-692 ◽  
Author(s):  
Enrique Galvez ◽  
Isabel Iriepa ◽  
Antonio Lorente ◽  
Jose Miguel Mohedano ◽  
Feliciana Florencio ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Carbon Atom ◽  
Mass Spectra ◽  
The Other ◽  
Reaction Conditions ◽  
Schiff’S Base ◽  
Triclinic Space Group ◽  
X Ray ◽  
H Nmr ◽  
Cell Dimensions

Reaction of 8-aminoquinoline with pyridine-2-carboxaldehyde (2), pyridine-3-carboxaldehyde (3), pyridine-4-carboxaldehyde (4), and benzaldehyde (5) yields the corresponding aminals or Schiff's bases according to reaction conditions; analogous results are obtained from the reaction of 1-amino-naphtalene with pyridine-2-carboxaldehyde (6). On the other hand, reaction of 8-aminoquinoline with thiophene-2-carboxaldehyde or pyrrole-2-carboxaldehyde yields neither the aminal nor the Schiff's base. Crystals of 4 (C24H19N5) belong to the triclinic space group [Formula: see text]. Cell dimensions are a = 11.547(3), b = 11.759(2), c = 15.687(5) Å, α = 98.50(2)°, β = 101.61(2)°, γ = 107.28(2)°, V = 1942.6(9) Å3. Final R = 0.077 and Rw = 0.064; 3160 reflections were observed. The ir, 1H nmr of 2–6, the mass spectra of 4 and 5 and the X-ray analysis of 4 are described and discussed. Preparative features, ir, 1H nmr, analyses and crystal structure indicate that the formation of 2–6 are governed mainly by the nucleophilicity at the aldehyde carbon atom and the existence of the hydrogen bonds in the aminal.

Darstellung, Reaktivität und Kristallstruktur von [(CO)3Mn(dppm)2(μ-S)Rh(CO)] / Synthesis, Reactivity and Crystal Structure of [(CO)3Mn(dppm)2(μ-S)Rh(CO)]

1992 ◽  
Vol 47 (5) ◽  
pp. 668-674 ◽  
Author(s):  
O. Heyke ◽  
G. Beuter ◽  
I.-P. Lorenz
Keyword(s):  
Crystal Structure ◽  
Mass Spectra ◽  
Frame Structure ◽  
Dimeric Complex ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Group 2

The reaction of [(CO)3Mn(dppm)2Rh(CO)] (1) with H2S in dichloromethane yields [(CO)3Mn(dppm)2(μ-S)Rh(CO)] (2), which is characterized by IR, 31P{1H}, 1H, 13C{1H} nmr and mass spectra. The crystal structure of 2 was determined by X-ray diffraction: space group P21/n, Z = 4, a = 1232.6(3), b = 2558.8(4), c = 1640.8(2) pm, β = 97.74(2)°, R/Rw = 0.048/0.057. The dimeric complex shows A-frame structure possessing a bridging sulfur and a semibridging CO group. 2 cannot be oxidized to the corresponding SO2 bridged complex [(CO)3Mn(dppm)2(μ-SO2)Rh(CO)] (3). The reaction of 2 with SO2, however, yields the SO2 bridged complex [(CO)2Mn(dppm)2(μ-S)(μ-SO2)Rh(CO)] (5); in dichloromethane 2 is readily chlorinated to afford the salt [(CO)3Mn(dppm),(μ-S)RhCl]Cl (4).

Bisophenol Flukicides. II. The Crystal Structure of 2,2'-(2,2,2-Trichloroethylidene)bis(4-chloro-6-nitrophenol)

1980 ◽  
Vol 33 (1) ◽  
pp. 77 ◽  
Author(s):  
D Hay ◽  
P Demunk ◽  
M Mackay
Keyword(s):  
Crystal Structure ◽  
Carbon Atom ◽  
Title Compound ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Aromatic Carbon ◽  
Space Group ◽  
Cell Dimensions ◽  
Phenyl Rings

Crystals of the title compound, C14H7Cl5N2O6, belong to the monoclinic space group P21/c with cell dimensions a 13.021(2), b 10.508(2), c 13.360(2)Ǻ, β 106.00(1)° and Z 4. The structure was solved by direct methods from diffractometer data measured with Cu Kα radiation, and refined to a conventional R index of 0.046 for 2465 non-equivalent terms. The phenyl rings are mutually inclined at 73.9ˌ, and the equivalent substituents of each ring lie on the same side of the plane formed by the bridging carbon atom and its two bonded aromatic carbon atoms.

Crystal structure of an inclusion complex between chiral monoaza-15-crown-5 and S(–)-1-phenyl-ethyl ammonium percholorate

2003 ◽  
Vol 218 (5) ◽  
Author(s):  
Süheyla Özbey ◽  
F. B. Kaynak ◽  
M. Toğrul ◽  
N. Demirel ◽  
H. Hoşgören
Keyword(s):  
Crystal Structure ◽  
Inclusion Complex ◽  
Single Crystal ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
New Type

AbstractA new type of inclusion complex, S(–)-1 phenyl ethyl ammonium percholorate complex of R-(–)-2-ethyl - N - benzyl - 4, 7, 10, 13 - tetraoxa -1- azacyclopentadecane, has been prepared and studied by NMR, IR and single crystal X-ray diffraction techniques. The compound crystallizes in space group

Mass spectra of 4,4-dimethyl-A-homo-4a,6-cholestadien-3-ols, 4,4-dimethyl-A-homo-5-cholestene-3,4a-diols and their derivatives

1982 ◽  
Vol 47 (10) ◽  
pp. 2768-2778
Author(s):  
Antonín Trka ◽  
Helena Velgová
Keyword(s):  
Carbon Atom ◽  
Electron Impact ◽  
Mass Spectra ◽  
Molecular Ions

Partial electron impact induced mass spectra are given of 3α-hydroxy-, 3β-hydroxy-, 3β-methoxy-, 3α-acetoxy- and 3β-acetoxy-4,4-dimethyl-A-homo-4a,6-cholestadienes, 3α,5α-epoxy-4,4-dimethyl-A-homo-5-cholestane, isomeric 4,4-dimethyl-A-homo-5-cholestene-3α(β),4aα(β)-diols, their 3-acetoxy derivatives and 3-methyl ethers. The fragmentation of the molecular ions of these substances involves the usual elimination of substituents (in the form of H2O, CH3OH, CH3COOH, CH2CO), but the most abundant and characteristic ions are products of the contraction of ring A (to a six- or five-membered one), accompanied by expulsion of a fragment containing the carbon atom C(4) with both methyls.

scholarly journals Molekül- und Kristallstruktur von 1.1-Dimethylsilylentitanocendichlorid, (CH3)2Si(C5H4)2TiCl2 / Molecular and Crystal Structure of l,r-Dimethylsilylene Titanocene Dichloride, (CH3)2Si(C5H4)2TiCl2

1981 ◽  
Vol 36 (10) ◽  
pp. 1208-1210 ◽  
Author(s):  
Hartmut Köpf ◽  
Joachim Pickardt
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Structure Determination ◽  
Titanocene Dichloride ◽  
Molecular And Crystal Structure ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Space Group ◽  
X Ray ◽  
Structural Dimensions

Abstract The molecular structure of the bridged [1]-titanocenophane 1,1'-dimethylsilylene titanocene dichloride, (CH3)2Si(C5H4)2TiCl2, has been investigated by an X-ray structure determination. Crystal data: monoclinic, space group C2/c, Z = 4, a = 1332.9(3), 6 = 988.7(3), c = 1068.9(3) pm, β = 113.43(2)°. The results are compared with the structural dimensions of similar compounds: 1,1'-methylene titanocene dichloride, CH2(C5H4)TiCl2, with the unbridged titanocene dichloride, (C5H5)2TiCl2 and the ethylene-bridged compound (CH2)2(C5H4)2TiCl2

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