Triferrocenylborane – Molecular Structure in Solution and in the Solid State

1995 ◽  
Vol 50 (2) ◽  
pp. 201-204 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Udo Dörfler ◽  
Wolfgang Milius ◽  
Max Herberhold
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Low Temperature ◽  
Single Crystal ◽  
Nmr Spectra ◽  
The Other ◽  
X Ray ◽  
Single Diastereomer ◽  
Structure In Solution ◽  
C Nmr

According to a single crystal X-ray structure determination all three ferrocenyl substituents of triferrocenylborane (1) adopt the same orientation with respect to the BC3-plane [P21/c monoclinic; Z = 4; a = 1353.5(3), b = 1695.6(3), c = 1056.4(2) pm, β = 109.27(3)°]. The simulated X-ray powder pattern of the single crystal is identical with the powder diagram of a macroscopic sample, indicating the presence of a single diastereomer (1a) in the solid state. However, at low temperature (< - 95 °C) in solution, the 13C NMR spectra suggest the presence of the second diastereomer (1b) in which one ferrocenyl group is oriented opposite to the other two with respect to the central BC3-plane.

Synthesis and Crystal Structures of Dimethylsilylene-Bridged (Amidocyclopentadienyl)dichlorotitanium(IV) Complexes with Various Substituents on the Cyclopentadienyl Ligand

2001 ◽  
Vol 66 (4) ◽  
pp. 605-620 ◽  
Author(s):  
Jaroslav Zemánek ◽  
Petr Štěpnička ◽  
Karla Fejfarová ◽  
Róbert Gyepes ◽  
Ivana Císařová ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Single Crystal ◽  
Spectral Methods ◽  
Nmr Spectra ◽  
Bulky Substituent ◽  
State Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cyclopentadienyl Ligand

(Amidocyclopentadienyl)dichlorotitanium(IV) complexes of the general formula [TiCl2{η5:η1(N)-C5(1-SiMe2Nt-Bu-2,3,4-Me3-5-R)}], where R = H (6b), Ph (6c), 4-fluorophenyl (6d) and 1-methylallyl (6e) were synthesized and characterized by spectral methods. Solid-state structure of [TiCl2{η5:η1(N)-C5Me4(SiMe2Nt-Bu)}] (6a) and 6d determined by single-crystal X-ray diffraction showed that variation of the ring substituent R has only a negligible effect on the molecular structure of the complexes. The NMR spectra indicate that motion of the bulky substituent R in compounds 6c, 6d and 6e is hindered below ca 50 °C.

Syntheses, Structures, and Spectroscopic Properties of Alkoxide, Hydroxide, and Siloxide Complexes with (η3-Allyl)Mo Moieties

1999 ◽  
Vol 54 (4) ◽  
pp. 473-481 ◽  
Author(s):  
Cornelia Borgmann ◽  
Christian Limberg ◽  
László Zsolnai ◽  
Katja Heinze
Keyword(s):  
Solid State ◽  
Low Temperature ◽  
Single Crystal ◽  
Nmr Spectra ◽  
Room Temperature ◽  
2D Nmr ◽  
Spectroscopic Properties ◽  
State Structure ◽  
X Ray ◽  
2D Nmr Spectra

Salts with binuclear anions of the general formula [(η3-C3H4R)(CO)2Mo(μ-OR′)2(μ-OR″)-Mo(CO)2(η3-C3H4R)]- (R = h , R′, R″ = Me, 2 ; R = CH3, R′ = CH(CH3)2, R″ = OH, 3; R = CH3, R′ = OH, R″ = OSiMe3, 4) have been synthesised via reaction of [(η3-C3H4R)- Mo(CO)2(CH3CN)2(thf)]+BF4- , 1, with NaOMe, NaOiPr, and KOSiMe3. All products were characterised spectroscopically and investigated by single crystal X-ray analysis. In the case of 3 low temperature 2D-NMR spectra revealed that the solid state structure is maintained in solution and that the compound shows a trigonal twist-rearrangement at room temperature.

The structure of 2,2-dibutyl-1,3,2-dioxastannane in the solid state and in solution

1992 ◽  
Vol 70 (1) ◽  
pp. 197-204 ◽  
Author(s):  
T. Bruce Grindley ◽  
Rasiah Thangarasa ◽  
Pradip K. Bakshi ◽  
T. Stanley Cameron
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Carbon Atom ◽  
Low Temperature ◽  
Nmr Spectra ◽  
Monomer Unit ◽  
The Other ◽  
Mirror Plane ◽  
X Ray ◽  
X Ray Crystallography

Crystals of 2,2-dibutyl-1,3,2-dioxastannane (1) are orthorhombic, of space group Pnma, with a = 7.663(3), b = 18.437(2), c = 9.277(4) Å, Z = 4, R = 0.0568 (Rw = 0.0551) for 1183 independent reflections with I > 3σ(I). Compound 1 is a polymer in which each monomer unit is joined to the next by a four-membered (SnO)2 ring. The Sn—O bond lengths inside the monomer units average 2.04 Å while those between monomers average 2.57 Å. The mirror plane of the crystal contains the atoms in the four-membered rings and the other oxygen atoms. Two of the three remaining carbon atoms in the six-membered rings of the monomer units are close to the mirror plane. The other carbon atom is disordered above and below the plane. It was shown by 119Sn NMR spectroscopy that solutions of 1 contain mixtures of oligomers that consist mainly of dimers, trimers, and tetramers in chloroform-d. ΔG0 values for dimmer–trimer equilibria and dimmer–tetramer equilibria of −2.5 and −1.5 kcal mol−1 were obtained from integration of low temperature 119Sn NMR spectra. These values favour the higher oligomers slightly less than those for 2,2-dibutyl-1,3,2-dioxastannolane. Keywords: 1,3,2-dioxastannanes, stannylene acetals. X-ray crystallography, 119Sn NMR spectroscopy.

Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Komplexe / Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Complexes

2002 ◽  
Vol 57 (9) ◽  
pp. 1017-1026 ◽  
Author(s):  
Herbert Schumann ◽  
Susanne Stenz ◽  
Frank Girgsdies ◽  
Stefan H. Mühle
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
X Ray ◽  
Tert Butyl ◽  
New Compounds ◽  
C Nmr

Ru3(CO)12 reacts with 1-tert-butyl-2,4-cyclopentadiene (1), 1-trimethylsilyl-2,4-cyclopentadiene (2), 1-tert-butyl-3-methyl-2,4-cyclopentadiene (3), 1,3-di(tert-butyl)-2,4-cyclopentadiene (4), 1-iso-propyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (5), 1-tert-butyl-2,3,4,5-tetramethyl- 2,4-cyclopentadiene (6), 1-phenyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (7), 2,5- diphenyl-2,4-cyclopentadiene (8), or 2,3,4,5-tetraphenyl-2,4-cyclopentadiene (9) with formation of the corresponding bis[dicarbonyl(cyclopentadienyl) ruthenium(I)] complexes [RuCp# (CO)2]2 1a to 9a. The 1H and 13C NMR spectra of the new compounds 3a and 5a to 9a as well as the single crystal X-ray structures of 1a, 4a, 5a, 7a, 8a, and 9a are reported and discussed

The relative stabilities of PhE(NH-t-Bu)2 and PhE(μ-N-t-Bu)2EPh (E = As, Sb, and Bi): X-ray structures of {Li2[PhAs(N-t-Bu)2]}2 and PhE(μ-N-t-Bu)2EPh (E = Sb, Bi)

2003 ◽  
Vol 81 (2) ◽  
pp. 169-174 ◽  
Author(s):  
Glen G Briand ◽  
Tristram Chivers ◽  
Masood Parvez
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Phenyl Group ◽  
Synthetic Approach ◽  
Relative Stabilities ◽  
X Ray ◽  
X Ray Crystallography ◽  
In Trans ◽  
C Nmr

The reaction of PhECl2 with 2 equiv of LiHN-t-Bu has been studied for the series E = As, Sb, and Bi to determine the effect of the phenyl group on subsequent amine condensation processes. For PhAsCl2, the metathesis product PhAs(NH-t-Bu)2 4 was obtained as a colourless oil. Similar reactions involving PhECl2, where E = Sb or Bi, yielded the cyclodipnict(III)azanes PhE(μ-N-t-Bu)2EPh 5 (E = Sb) and 6 (E = Bi), respectively. Treatment of 4 with 2 equiv of n-BuLi produced the dilithium salt Li2[PhAs(N-t-Bu)2] 7a. Products 4, 5, 6, and 7a were characterized by 1H, 7Li (7a), and 13C NMR spectra, while 5, 6, and 7a were also structurally characterized by X-ray crystallography. Compound 7a is dimeric in the solid state via intermolecular Li···N and η6-Li···Ph interactions. The cyclodipnict(III)azanes 5 and 6 have similar structures, with the exocyclic phenyl groups in trans positions relative to the E2N2 ring. This synthetic approach provides a new route to the four-membered rings RE(μ-N-t-Bu)2ER (E = Sb, Bi) and the first example of a bis(organyl)cyclodibism(III)azane.Key words: arsenic, antimony, bismuth, amides, imides.

The Crystal and Molecular Structure of Dinitrato(triphenylphosphine)mercury(II)

1974 ◽  
Vol 52 (2) ◽  
pp. 198-202 ◽  
Author(s):  
Simon H. Whitlow
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Crystal And Molecular Structure ◽  
Bond Distance ◽  
The Other ◽  
Tetrahedral Coordination ◽  
X Ray ◽  
R Factor ◽  
Computer Controlled ◽  
Distorted Tetrahedral Coordination

The structure of dinitrato(triphenylphosphine)mercury(II), Hg(N03)2.P(C6H5)3, has been determined from single–crystal X-ray data measured on a computer–controlled diffractometer. The crystals are monoclinic, have a unit cell of dimensions a = 10.39(1), b = 9.56(1), c = 19.44(2) Å, β = 94.3(1)°, which contains 4 molecules, and they belong to the space group, P21/c. The structure has been refined by least–squares methods from 2470 independent observed reflections to a conventional R-factor of 0.061. The Hg atom has a distorted tetrahedral coordination with Hg—O bond lengths of 2.190(8), 2.428(8), and 2.560(9) Å and an Hg—P bond distance of 2.359(3) Å. There are 2 distinct types of NO3 groups bonded to Hg. One is an unshared, unidentate ligand and the other acts as a bridging group joining 2 Hg atoms. Chains of—Hg—NO3—Hg—atoms are formed which follow crystallographic two-fold screw axes in the b-direction.

On Attempts to Synthesize Lanthanide Complexes of the Dianionic Fluorenyl-alkoxo Ligand [C13H8-cyclo-C6H10-O]2-. Crystal Structure of (C13H9-cyclo-C6H10-O)LaI2(DME)2

2003 ◽  
Vol 58 (5) ◽  
pp. 389-394 ◽  
Author(s):  
Alexander A. Trifonov ◽  
Mikhail N. Bochkarev ◽  
Herbert Schumann ◽  
Sebastian Dechert
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Ir Spectra ◽  
Single Crystal ◽  
Lanthanide Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Elemental Analyses ◽  
C Nmr

Racemic trans-2-(9(H)-fluoren-9-yl)cyclohexanol, C13H9-cyclo-C6H10-OH (1), reacts with two equivalents of potassium naphthalenide in THF to give the dipotassium salt [C13H8-cyclo-C6H10-O]- K2(THF) (2). Recrystallization of 2 from pyridine affords the solvent free salt [C13H8-cyclo-C6H10- O]K2 (3). The reactions of LaI3(THF)4 with one equivalent of 2 or of YbI2(THF)2 with equimolar amounts of 2 produce the alkoxolanthanum diiodide (C13H9-cyclo-C6H10-O)LaI2(DME)2 (4) and the ytterbium dialkoxide (C13H9-cyclo-C6H10-O)2Yb(THF)0.5(5), respectively. [(Me3Si)2N]3Y reacts with three equivalents of 1 with elimination of hexamethyldisilazane and formation of the yttrium trialkoxide (C13H9-cyclo-C6H10-O)3Y (6). The compounds 2 to 5 were characterized by elemental analyses, 1H NMR, 13C NMR and IR spectra. The molecular structure of 4 was determined by single crystal X-ray diffraction.

Binuclear Fulvalene and Bis(cyclopentadienyl)methane Halfsandwich Complexes of Manganese and Rhenium Containing Tetrahydrothiophene Ligands. X-Ray Structure Analysis of {(CO)2Mn[C5H4-C5H4]Mn(CO)2}(μ-SC4H8)

1993 ◽  
Vol 48 (2) ◽  
pp. 161-170 ◽  
Author(s):  
Max Herberhold ◽  
Martin Biersack ◽  
Thomas E. Bitterwolf ◽  
Arnold L. Rheingold
Keyword(s):  
Molecular Structure ◽  
Ir Spectra ◽  
Structure Analysis ◽  
Nmr Spectra ◽  
X Ray ◽  
Carbonyl Ligands ◽  
Tetrahydrofuran Solution ◽  
C Nmr

AbstractThe photo-induced substitution of carbonyl ligands in the binuclear cyclopentadienyl-type complexes (CO)3M[C5H4(CH2)nC5H4]M(CO)3 (n = 0 (fulvalene), M = Mn (1) and Re (2); n = 1 (bis(cyclopentadienyl)methane), M = Mn (3) and Re (4)) has been studied in the presence of tetrahydrothiophene, SC4H8 (tht). Photodecarbonylation of 1 - 4 in tetrahydrofuran solution leads to solvent-stabilized intermediates which react with tht in the dark to give monosubstituted derivatives (CO)3M[C5H4(CH2)nC5H4]M(CO)2(tht) (1a - 4a). In the case of M = Mn, thtbridged compounds {(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2}(μ-tht) (n = 0 (1b) and n = 1 (3b)) are also obtained which are the exclusive products of the photolysis of 1 and 3 in benzene in the presence of tht. Photodecarbonylation of 1 - 4 in neat tetrahydrothiophene produces disubstituted derivatives in the case of manganese, (tht)(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2(tht) (n = 0 (1c) and n = 1 (3c)), whereas only the monosubstituted complexes 2a and 4a could be isolated in the case of rhenium. The molecular structure of the tht-bridged fulvalene complex 1b has been determined by an X-ray structure analysis. A special reaction of dimethyl disulfane with the photolyzed tetrahydrofuran solution of 2 leads to the bis(methylthiolato) compound (CO)3Re[C5H4- C5H4]Re(CO)(SMe)2 (5). The new complexes were characterized by their IR spectra v(CO) and their 1H and 13C NMR spectra.

Interactions de l'ion Ag+ avec la glutarimide

1984 ◽  
Vol 62 (7) ◽  
pp. 1287-1291 ◽  
Author(s):  
Johanne Perron ◽  
André L. Beauchamp
Keyword(s):  
Infrared Spectroscopy ◽  
Infrared Spectrum ◽  
Nmr Spectra ◽  
The Other ◽  
Mirror Plane ◽  
Bond Orders ◽  
X Ray Diffraction ◽  
Complex Species ◽  
X Ray ◽  
C Nmr

The 1:1 complex formed between Ag+ ions and glutarimide was investigated by X-ray diffraction, infrared spectroscopy, and 1H and 13C nmr. The crystals are monoclinic, C2/c, a = 13.497(3) Å, b = 9.503(2) Å, c = 9.600(4) Å, β = 92.30(3)°, Z = 4 molecules per cell. The structure was refined on 1086 nonzero [Formula: see text] reflections to R = 0.027. One half of the Ag atoms are linearly coordinated to the N atoms of two deprotonated glutarimide ligands, whereas the other half are surrounded by an approximate tetrahedron of four carbonyl oxygens belonging to two adjacent [Glu–Ag–Glu]− units. The [Glu–Ag–Glu]− groups are joined by tetrahedrally coordinated Ag atoms into infinite chains along the c axis. Complexation introduces a number of changes in the infrared spectrum of glutarimide. They can be related to the disappearance of the N—H vibrator and the change of bond orders in the —C(O)—N—C(O)— portion of the ligand. The nmr spectra show that coordinated glutarimide retains a mirror plane when the Ag complex is dissolved in DMSO. This suggests that the O-bonded Ag atoms dissociate to a large extent in solution, leaving the linear [Glu–Ag–Glu]− ions as the major glutarimide complex species.

The Structure of 1,3-Enaminoketonatoboron Difluorides in Solution and in the Solid State

2003 ◽  
Vol 56 (12) ◽  
pp. 1209 ◽  
Author(s):  
Kuniaki Itoh ◽  
Kazuhiko Okazaki ◽  
Miki Fujimoto
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Electron Distribution ◽  
Chelate Ring ◽  
Chemical Shifts ◽  
Electron System ◽  
The Other ◽  
13C Nmr Spectra ◽  
X Ray ◽  
Tautomeric Forms

Nuclear magnetic resonance, infrared, and ultraviolet spectra and X-ray analysis of three 1,3-enaminoketonatoboron difluorides (BF2 complexes, (2a)–(2c)) both in solution and in the solid state have been recorded. Their structures are discussed in relation to the electron distribution in their chelate rings and in comparison with those of their parent compounds (1a)–(1c) and 1,3-diketonatoboron difluorides. C1 and C3 chemical shifts in the 13C NMR spectra indicated that the ketoamine and enolimine tautomeric forms may be present in equal amounts. Additionally, the phenyl groups participate in the delocalized π-electron system of the chelate ring. On the other hand, in the solid state, a comparison of the bond lengths by X-ray analysis provides information on processes occurring as contribution of the enolimine form increases. The information found may offer valuable suggestions for the reactivity and the structure of the products for the reactions of the BF2 complexes.

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