The triethylammonium-pyridine complex cation

Borah, Bhargab; Wood, John L.

doi:10.1016/0022-2860(74)85150-1

Cited by 7 publications

(5 citation statements)

References 9 publications

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“…The observed v(NH) absorption is not a single peak but a complex multicomponent absorption extending over at least 400 cm-' of the spectrum; the full extent and complexity of this absorption, and of the corresponding v(ND) absorption in deuterated material, become evident at low temperatures (3,6,7). Similar observations have been made with other alkylammonium salts (8)(9)(10)(11)(12)(13)(14). While general explanations of this complexity have been advanced (4, 5 , 8) (see below), the frequency-distance correlation was not pursued in any detail, both because of lack of accurate structural information on the three halides at the time and because of the uncertainty as to how to extract from each spectrum a single v(NH) or v(ND) frequency value to be used in such a correlation.…”

supporting

confidence: 86%

“…That Fermi resonance perturbations are responsible for the complexity has been concluded also from the observation that the NH stretching absorption in the solution spectra of Et,NHt salts is independent of the solvent (1 1, 14) and from the study of the ir spectra of the trimethylammonium-pyridine and triethylammonium-pyridine complex cations (9,10). On this view the complexity of the NH and ND stretching absorptions in Et3NHX arises from overtones and binary combinations of fundamental vibrations of the cations in the 1000-1500 cm-' region, enhanced by extensive Fermi resonance with the NH or ND stretching fundamental.…”

Section: Comparison With Me3nhxmentioning

confidence: 95%

“…Sandorfy et al (4,5) and Lord and McDowell (3,6,7) made this observation with Et3NHX, and Ebsworth and Sheppard (8) with Me,NDI, some 25 years ago. The studies that have been published since, both on triethylammonium (10,11,14,21,22), trimethylammonium (9,(23)(24)(25), and higher trialkylammonium (21) halides bear witness to the continued interest in this phenomenon, and are not confined to the simple halides but include other alkylammonium salts as well (12,13). The complex NH and ND stretching absorptions persist, with band sharpening and increased detail, down to liquid-helium temperature (3,6) and are observed also in solution spectra of these salts (9-11, 14, 21, 22).…”

Section: Comparison With Me3nhxmentioning

confidence: 99%

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Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

James¹,

Cameron²,

Knop³

et al. 1985

Can. J. Chem.

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A crystal structure determination has shown that the ethyl groups in the three isostructural (P63mc, Z = 2) triethylammonium halides, Et3NHX (X = Cl, Br, I), at room temperature are orientationally disordered and the [Formula: see text] groups are linear by symmetry. The unusual extent and complexity of the NH and ND stretching absorptions in the ir spectra of all three compounds between 10 and 293 K are discussed in terms of Fermi resonance interactions. The centroid ν(NH) and ν(ND) frequencies extracted from the spectra correlate with the [Formula: see text] distances. It is shown that if Fermi resonance is the sole cause of the complexity of the stretching absorptions, then these centroids represent the ν(NH) and ν(ND) frequencies unperturbed by Fermi resonance. The centroid frequencies in the three halides are unusually low, pointing to strong [Formula: see text] hydrogen bonding.

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supporting

confidence: 86%

Section: Comparison With Me3nhxmentioning

confidence: 95%

Section: Comparison With Me3nhxmentioning

confidence: 99%

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Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

James¹,

Cameron²,

Knop³

et al. 1985

Can. J. Chem.

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“…Of course, the observed higher symmetry of 5 in solution could also arise from equilibria between different OH positions in 5b , which would be rapid with respect to the NMR time scale. In the IR spectrum of 5 a broad band of low intensity at 2710 cm -1 can be distinguished, which could arise from a proton coordinated to two basic centers (free Et 3 NH + has an absorption at 3150 cm -1 , while [Et 3 N···H···py] + absorbs around 2570 cm -1 ) . As can be deduced from single-crystal X-ray diffraction (see below), in the crystal 5 seems to adopt a bonding which is better described as 5b .…”

Section: Syntheses Of Phenyl-substituted Gallacyclosiloxanesmentioning

confidence: 94%

Cyclosiloxanes Containing a Gallium Atom as Ring Member from the Reaction of tert-Butoxygallane with Di- and Trisiloxanediols

2001

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tert-Butoxygallane, [tBuOGaH 2 ] 2 , reacts with tetraphenyl-1,3-disiloxanediol, HO(Ph 2 )Si-O-Si(Ph 2 )OH, with hydrogen elimination to form the bicyclic compound [(OSiPh 2 OSiPh 2 O)-[Ga(H)] 2 (OtBu) 2 ] (1). The skeleton of molecule 1 consists of a four-membered Ga 2 O 2 ring to which a five-membered O-Si-O-Si-O bridge is connected through Ga-O bonds. While the gallium atoms each have a hydrogen atom as further substituent, the oxygen atoms of the four-membered ring have tert-butyl substituents and the silicon atoms each bear two phenyl groups. When the reactant ratio is changed to [tBuOGaH 2 ] 2 :1,3-disiloxanediol ) 1:2, two new products are formed in almost equal amounts: [(OSiPh 2 OSiPh 2 OSiPh 2 O)GaH] 2 (2) and [(OSiPh 2 OSiPh 2 OSiPh 2 O)GaOtBu] 2 (3). Both compounds are centrosymmetric, forming either a central Ga 2 O 2 ring to which two eight-membered GaO 4 Si 3 rings are fused with two common GaO edges (2) or a central Ga 2 O 2 ring, the gallium corners serving as spiro centers for again eight-membered GaO 4 Si 3 rings (3). In comparison to 1, molecules 2 and 3 contain Si-O chains with one further SiO unit and have lost either tert-butyl alcohol (2) or hydrogen (3) with respect to 1. Compound 2 can also be obtained when, instead of tetraphenyl-1,3disiloxanediol, hexaphenyl-1,5-trisiloxanediol (HO(Ph 2 )SiOSiPh 2 OSi(Ph 2 )OH) is reacted with tert-butoxygalane. The central Ga 2 O 2 rings in molecules 2 and 3 originate from Lewis acid and base interactions but are of different stability. In 2, the ring is formed by oxygen atoms bearing a silicon substituent and therefore should have reduced basicity: consequently, 2 can be split (into halves) by simple reaction with triethylamine, the nitrogen atom serving as a donor to gallium. The product of this reaction is an eight-membered Si 3 O 4 Ga ring with hydrogen and triethylamine as ligands at gallium and two phenyl groups on each of the silicon atoms and has the formula [(OPh 2 SiOSiPh 2 OSiPh 2 O)GaH(NEt 3 )] (4). Further change of the stoichiometry between tert-butoxygallane and the 1,5-trisiloxanediol in favor of the silicon compound again has a consequence for the reaction products. Using NEt 3 as crystallization promotor gave [(OSiPh 2 OSiPh 2 OSiPh 2 O) 2 Ga‚HNEt 3 ] (5). In this compound a spiro-connected gallium atom is a member of two GaO 4 Si 3 rings. The triethylamine group is coordinating a proton which forms a bridge between an oxygen atom of the rings and nitrogen. Compound 5 can also be obtained from 2 using a dilute solution of water in THF. Compounds 1-5 have been fully characterized by 1 H, 13 C, 29 Si NMR and IRspectroscopy and have been the subject of single-crystal X-ray diffraction studies.

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“…The IR spectrum of solid 6 was complicated by the presence of absorptions due to the two cations [PPN] + and [NEt 3 H] + …”

Section: Methodsmentioning

confidence: 99%

Modeling the Formation of Molybdenum Oxides from Alkoxides: Crystal Structures of [Mo₄O₄Cl₄(μ₂-OEt)₄(HOEt)₂(μ₃-O)₂] and [PPN]⁺[Et₃NH]⁺[Cl₂(O)Mo(μ₂-O)₂Mo(O)Cl₂]²^-

Limberg¹,

Downs²,

Blake³

et al. 1996

Inorg. Chem.

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The reactions of the binuclear oxomolybdenum(V) complex [Cl(2)(O)Mo(&mgr;-OEt)(2)(&mgr;-HOEt)Mo(O)Cl(2)] (1) with Me(3)Si(allyl) and SbF(3) produce the compounds [Mo(6)O(6)Cl(6)(&mgr;(3)-O)(2)(&mgr;(2)-OEt)(6)(&mgr;(2)-Cl)(2)] (2) and [Mo(8)O(8)Cl(6)(&mgr;(3)-O)(4)(OH)(2)(&mgr;(2)-OH)(4)(&mgr;(2)-OEt)(4)(HOEt)(4)] (3), respectively. Treatment of 1 with the Lewis base PMe(3) affords the tetrameric complex [Mo(4)O(4)Cl(4)(&mgr;(2)-OEt)(4)(HOEt)(2)(&mgr;(3)-O)(2)] (4), which represents another link in the chain of clusters produced by the reactions of 1 and simulating the build-up of polymeric molybdenum oxides by sol-gel methods. The crystal structure of 4 has been determined [C(12)H(32)Cl(4)Mo(4)O(12), triclinic, P&onemacr;, a = 7.376(2) Å, b = 8.807(3) Å, c = 11.467(4) Å, alpha = 109.61(1) degrees, beta = 92.12(3) degrees, gamma = 103.75(2) degrees, Z = 1]. By contrast, reaction of 1 with the nitrogen base NEt(3), followed by treatment with [PPN]Cl.2H(2)O ([PPN](+) = [Ph(3)P=N=PPh(3)](+)), gives the complex [PPN](+)[Et(3)NH](+)[Cl(2)(O)Mo(&mgr;(2)-O)(2)Mo(O)Cl(2)](2)(-) (6) in 90% yield. Its crystal structure [C(36)H(30)Cl(4)MoNOP(2), triclinic, Pna2(1), a = 21.470(6) Å, b = 16.765(2) Å, c = 9.6155(14) Å, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, Z = 16] includes the anion [Cl(2)(O)Mo(&mgr;(2)-O)(2)Mo(O)Cl(2)](2)(-), which is a charged derivative of the species forming the gels in sol-gel processes starting from chloromolybdenum ethoxides. Furthermore, compound 1 is found to be catalytically active in esterification and dehydration reactions of alcohols.

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The triethylammonium-pyridine complex cation

Cited by 7 publications

References 9 publications

Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

Cyclosiloxanes Containing a Gallium Atom as Ring Member from the Reaction of tert-Butoxygallane with Di- and Trisiloxanediols

Modeling the Formation of Molybdenum Oxides from Alkoxides: Crystal Structures of [Mo₄O₄Cl₄(μ₂-OEt)₄(HOEt)₂(μ₃-O)₂] and [PPN]⁺[Et₃NH]⁺[Cl₂(O)Mo(μ₂-O)₂Mo(O)Cl₂]²^-

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The triethylammonium-pyridine complex cation

Cited by 7 publications

References 9 publications

Triethylammonium halides, Et3NHX (X = Cl, Br, I): simple structure, complex spectrum

Triethylammonium halides, Et3NHX (X = Cl, Br, I): simple structure, complex spectrum

Cyclosiloxanes Containing a Gallium Atom as Ring Member from the Reaction of tert-Butoxygallane with Di- and Trisiloxanediols

Modeling the Formation of Molybdenum Oxides from Alkoxides: Crystal Structures of [Mo4O4Cl4(μ2-OEt)4(HOEt)2(μ3-O)2] and [PPN]+[Et3NH]+[Cl2(O)Mo(μ2-O)2Mo(O)Cl2]2-

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Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

Triethylammonium halides, Et₃NHX (X = Cl, Br, I): simple structure, complex spectrum

Modeling the Formation of Molybdenum Oxides from Alkoxides: Crystal Structures of [Mo₄O₄Cl₄(μ₂-OEt)₄(HOEt)₂(μ₃-O)₂] and [PPN]⁺[Et₃NH]⁺[Cl₂(O)Mo(μ₂-O)₂Mo(O)Cl₂]²^-