Vibrational spectra of the boron halides and their molecular complexes. Part 11. Complexes of boron trifluoride with phosphine and its methyl derivatives. An ab initio study

Ab initio calculations, at the second-order level of M?ller-Plesset perturbation theory, using a triple-zeta Gaussian basis set with polarization and diffuse functions on all atoms, have been carried out on the donor-acceptor complexes of boron trifluoride with phosphine and its mono-, di-, and trimethyl derivatives. The structures, interaction energies, and vibrational spectra of the complexes were determined. The preferred conformer was found to be the staggered species in each case. The computed data were compared with those for some similar complexes containing boron trifluoride and a series of related oxygen, sulfur, and nitrogen bases, and the effect of successive methyl substitution in each series was investigated.     

The vibrational spectra of the boron halides and their molecular complexes, part 5 An ab initio study of the infrared spectrum of the boron trifluoride-carbon dioxide complex

The optimized structures, interaction energies, Mulliken charges and vibrational spectra of three conformers of a 1:1 complex between boron trifluoride and carbon dioxide have been determined by means of ab initio calculations at the second-order level of M?ller-Plesset perturbation theory, using the 6-31G* basis set. All three structures feature a B⋯O electron donor-acceptor interaction. One of the structures, in which the carbon dioxide axis eclipses one of the BF bonds, was found to be a genuine minimum, one (the corresponding staggered form) a first-order saddle point and the third (a linearly bonded B⋯OCO species) a second-order transition state. The computed infrared spectrum of the preferred conformer has been used to predict the appearance of the spectrum of boron trifluoride and carbon dioxide co-deposited in cryogenic matrices, which will be reported in a forthcoming publication. Received: 18 November 1996 / Accepted: 11 March 1997     

The vibrational spectra of the boron halides and their molecular complexes. Part 13. Ab initio studies of the complexes of boron trifluoride with formaldehyde and some of its analogs

The structure, the interaction energy, and the vibrational spectrum of the electron donor–acceptor complex formed between boron trifluoride, as a Lewis acid, and formaldehyde, as a Lewis base, have been determined by means of ab initio calculations at the second‐order level of Møller–Plesset perturbation theory, using a triple‐zeta basis set with polarization and diffuse functions on all atoms. The object was to examine the differences in the properties of the complexes formed between boron trifluoride and an oxygen base containing oxygen in the sp² hybrid state with those of some sp³ oxygen bases studied earlier. The investigation has then been extended to include the related bases thioformaldehyde and methanimine, to assess the effect of substituting the oxygen atom by a sulphur atom or an imino group. A further range of formaldehyde analogs, containing one and two methyl groups, one and two fluorine atoms, and one methyl group and one fluorine atom, has also been included. The preferred structure of each complex has been identified. The computed data have been compared, and the complex properties correlated with some relevant physical properties of the bases. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Donor-acceptor complexes of linear oligopyrroles with boron trifluoride. Spectral studies and quantum-chemical simulation

Intermediate products of synthesis of the boron trifluoride complexes with linear oligopyrroles are found. By means of electronic spectroscopy it was shown that the reaction of linear oligopyrroles with boron trifluoride in solutions resulted in the formation of stable donor-acceptor complexes. Their composition was established and the formation constants were evaluated. It was shown that transformation of these complexes in the corresponding borofluoride complexes is possible only while boiling the reaction mixture. By means of quantum-chemical methods the structural and energy parameters of the donor-acceptor complexes under study were calculated.     

Synthetic utility and mechanistic implications of the Fries rearrangement of hydroquinone diesters in boron trifluoride complexes

Reactions of boron trifluoride methyl and ethyl etherate complexes with hydroquinone diesters yield monomethyl and monoethyl derivatives of acetylhydroquinones. The use of sterically hindered boron trifluoride etherate complexes results in acetylhydroquinone derivatives. This procedure represents a one-step synthesis of acetylhydroquinone derivatives, important building blocks for a variety of synthetic applications.     

Polymerization of coordinated monomers. XXII. Ab initio molecular orbital study on the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride as a model of growing radical end

The geometrical and electronic structures of the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride were determined by using an ab initio molecular orbital method. The 2-methoxycarbonyl propyl radical complex was a model of the growing radical end in the copolymerization of methyl methacrylate in the presence of boron halides. The most stable structure of the binary radical complex composed of 2-methoxycarbonyl propyl radical with boron trichloride was a twisted form in which the dihedral angle between the vinyl group and the ester group was 32°, while that of the binary radical complex composed of methyl methacrylate radical with boron trifluoride was a planar form as the free radical. The frontier orbital energy of 2-methoxycarbonyl propyl radical was lowered by 0.06 au by the coordination of boron trichloride, while that was lowered only by 0.02 au by the coordination of boron trifluoride. The polymerization mechanism was elucidated on the basis of these predictions. © 1993 John Wiley & Sons, Inc.     

A proton magnetic resonance study of complexes of pyridine, 2-methylpyridine 3-methylpyridine, 4-methylpyridine,and 2,6-dimethylpyridine with borane and boron trifluoride

A variable temperature, proton magnetic resonance study has been made of complexes of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2,6-dimethylpyridine with borane and boron trifluoride. By lowering the temperature and slowing ligand exchange, separate resonance signals can be observed for bulk and complexed molecules of the base. A direct comparison of the complexing abilities of these ligands was made by studying them in pairs with borane or boron trifluoride. The complexing abilities, as estimated from the NMR data, decreased in the order: 4-MePy > 3-MePy > Py > 2-MePy > 2,6-MePy. This trend was interpreted in terms of steric effects and the basic strengths of these molecules towards boron trifluoride.     

Donor-acceptor complexes of dipyrrolylmethenes with boron trifluoride as intermediates in the synthesis of Bodipy

The formation of donor-acceptor complexes of dipyrrolylmethene and structurally similar biladiene-a,c with boron trifluoride was studied by electronic absorption, IR, and ¹H NMR spectroscopies as well as by quantum chemical calculations. It was shown that the formation of donor-acceptor complexes is the first step of the synthesis of the corresponding boron fluoride chelate complexes (Bodipy). The hydrogen bond N—H...F—B additionaly stabilizes the donor-acceptor complexes. The stability constants, geometric parameters, and energy characteristics of the donoracceptor complexes were determined; the two-step mechanism of Bodipy synthesis was analyzed.     

Electron delocalization in 9-oxidophenalenone complexes of boron and beryllium

The preparation and characterization of a series of 9-oxidophenalenone (9-opo) complexes of beryllium and boron is reported. The structure of (9-opo)₂Be has been established by X-ray crystallographic analysis. The complexes have been studied with electrochemical techniques and electron spin resonance spectroscopy and evidence is presented for an unusual mode of electron delocalization (spiroconjugation) in the reduced species obtained from the bis (9-opo) complexes.     

Ab initio molecular orbital studies of the vibrational spectra of the van der Waals complexes of boron trifluoride with the noble gases

The molecular structures, interaction energies, charge transfer properties and vibrational spectra of the van der Waals complexes formed between boron trifluoride and the noble gases neon, argon, krypton and xenon have been computed using second and fourth order M?ller-Plesset perturbation theory and the Los Alamos National Laboratory LANL2DZ basis set. The complexes are all symmetric tops, with the noble gas atom acting as a sigma electron donor along the C3 axis of the BF3 molecule. The interaction energies are all vanishingly small, and the amount of charge transferred in each case is of the order of 0.01e. The directions of the wavenumber shifts of the symmetric bending (nu2) and antisymmetric stretching (nu3) modes of the BF3 fragment confirm those determined experimentally, and the shifts are shown to correlate well with the polarizability of the noble gas atom and the inverse sixth power of the intermonomer separation. The nu2 mode is substantially more sensitive to complexation than the nu3 vibration.     

Design,synthesis, and evaluation of unsymmetrical difluoro‐boron complexes with imidazoline as potential fungicides

A series of unsymmetrical difluoro‐boron(BF₂) complexes with pyridine and imidazoline were synthesized by reaction of new chelating ligands (arylmethyl‐imidazolidinylidene)‐pyridin‐2‐yl‐amine with boron trifluoride diethyl etherate. All the ligands and BF₂ complexes were structurally characterized by IR, HRMS, ¹H, ¹³C,¹¹B, and ¹⁹F NMR, indicating the bidentate complexation of imidazoline nitrogen and the pyridine nitrogen to the boron center. Evaluation of agricultural bioactivities showed that some of the BF₂ complexes exhibited moderate fungicidal activities, and most of the BF₂ complexes exhibited higher activities than the none‐BF₂ complexed substrates. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:418–424, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20567     

酚基吡啶硼配合物发光材料

主要介绍双酚基吡啶硼配合物的合成、分子结构、分子堆积结构及其在有机电致发光器件中的应用.研究结果表明一些双酚基吡啶硼配合物可以作为发光材料制备性能优良的电致发光器件.     

A new method for the synthesis of bishydroperoxides based on a reaction of ketals with hydrogen peroxide catalyzed by boron trifluoride complexes

A reaction of cycloalkanone, alkanone and alkyl aryl ketone ketals with H₂O₂ catalyzed by boron trifluoride etherate and boron trifluoride-methanol complexes was studied. A new versatile method for the synthesis of bishydroperoxides and their derivatives, viz. 1,1′-dihydroperoxyperoxides and 1,2,4,5-tetraoxacyclohexanes, was developed based on this reaction.     

Polymerization of coordinated monomers. XXI. Ab initio molecular orbital study on the binary molecular complex composed of methyl methacrylate and boron trifluoride

The stereo- and electronic structures of the binary molecular complex composed of methyl methacrylate and boron trifluoride are obtained by using an ab initio molecular orbital method with an STO-3G basis set. The total energy change on the binary molecular complex formation is ?1.3 X 10^?2 Hartree (?8.2 kcal/mol). The electron transfer from methyl methacrylate to boron trifluoride and the change in the energy level of the lowest unoccupied molecular orbital of methyl methacrylate on the complex formation with boron trifluoride are much smaller than those on the complex formation with boron trichloride. A twisted form in which the dihedral angle between the vinyl plane and the ester plane is 16.9° is the most stable structure of the binary molecular complex composed of methyl methacrylate and boron trifluoride. A strong bonding overlap population between a β-hydrogen of methyl methacrylate and a fluorine of boron trifluoride is found in this conformation. © 1992 John Wiley & Sons, Inc.     

Ferrocenyl-substituted Schiff base complexes of boron: synthesis, structural, physico-chemical and biochemical aspects

Biological important complexes of boron(III) derived from 1-acetylferrocenehydrazinecarboxamide (L1H), 1-acetylferrocenehydrazinecarbothioamide (L2H) and 1-acetylferrocene carbodithioic acid (L3H) have been prepared and investigated using a combination of microanalytical analysis, melting point, electronic, IR, 1H NMR and 13C NMR spectral studies, cyclic voltammetry and X-ray powder diffraction studies. Boron isopropoxide interacts with the ligands in 1:1, 1:2 and 1:3 molar ratios (boron:ligand) resulting in the formation of coloured products. On the basis of conductance and spectral evidences, tetrahedral structures for boron(III) complexes have been assigned. The ligands are coordinated to the boron(III) via the azomethine nitrogen atom and the thiolic sulfur atom/enolic oxygen atom. On the basis of X-ray powder diffraction study one of the representative boron complex was found to have orthorhombic lattice, having lattice parameters: a=9.9700, b=15.0000 and c=7.0000. Both the ligands and their complexes have been screened for their biological activity on several pathogenic fungi and bacteria and were found to possess appreciable fungicidal and bactericidal properties. Plant growth regulating activity of one of the ligand and its complexes has also been recorded on gram plant, and results have been discussed.     

New Synthetic Capabilities of Sulfonium Salts

The review summarizes published data on the synthesis and reactivity of new functionally substituted sulfonium salts: dimethyl(trifluoromethylsulfonyloxy)sulfonium trifluoromethanesulfonate, dimethyl(trifluoromethylsulfonyl)sulfonium trifluoromethanesulfonate, various disulfonium dications, dimethyl sulfidesulfur trioxide complex, acyl(dimethyl)sulfonium salts, dimethyl(trifluoroacetyl)sulfonium salts, and boron trifluoride complexes with alkylthio-substituted acyl fluorides as intramolecular analogs of acylsulfonium salts. A theoretical approach is described, which explains electrophilic reactivity of sulfonium salts.     

2,4-Difluoro anisole: a promising complexing agent for boron isotopes separation by chemical exchange reaction and distillation

Although methods of boron isotopes separation were intensively pursued about 60 years, the chemical exchange distillation is the only method that has been applied in industrial scale production of ¹⁰B. The present anisole BF₃ system suffers from the drawbacks like high melting point, relatively low separation coefficient and instability under reaction conditions, which demand a continuous search for more effective and efficient donors for boron isotope separation. A series of fluoro-substituted anisole derivatives were screened in this paper, among which 2,4-difluoro anisole exhibited good properties compared with anisole. Studies on the boron trifluoride and 2,4-difluoro anisole adduct, its thermodynamic and physical properties related to large-scale isotopic separation is reported. The results showed that 2,4-difluoro anisole is better than anisole in separation coefficient, freezing point and stability under pyrolysis conditions, which suggest a further detailed investigations on boron trifluoride and 2,4-difluoro anisole adduct.     

Synthesis and structures of boron complexes of acyl hydroxy coumarins

New boron chelates were synthesized by the reactions of 3-acetyl-4-hydroxycoumarin and 8-acyl-7-hydroxy-4-methylcoumarins with boron trifluoride etherate and hydroxybenzodioxaborole. The structure of 3-acetyl-4-difluoroboryloxycoumarin containing an intramolecular C=O...B coordination bond was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2012–2015, November, 2006.     

α-substituted boron difluoride acetylacetonates

By treatment of α-substituted acetylacetone derivatives with boron trifluoride etherate a series of earlier unknown boron difluoride complexes is obtained. The series includes binuclear complexes containing boron in the chelate fragment connected via sulfur or selenium atom. Gas chromatographic and spectral characteristics of the obtained compounds were investigated. By means of chromato-mass spectrometry their reaction with hydrazine in acidic and alkaline media was studied.     

Syntheses and remarkable photophysical properties of 5-(2-pyridyl) pyrazolate boron complexes; photoinduced electron transfer

A new series of pyridyl pyrazolate boron complexes 2a-e have been synthesized, in which 2a-c exhibit remarkable dual fluorescence properties due to the photoinduced electron transfer reaction.