Synthesis and Infrared and 1H, 13C, 119Sn NMR Spectra of Some Tris- and Bis(1-butyl)tin(IV) Naphthoates and Hydroxynaphthoates

1997 ◽  
Vol 62 (2) ◽  
pp. 279-298 ◽  
Author(s):  
Jaroslav Holeček ◽  
Milan Nádvorník ◽  
Karel Handlíř ◽  
Vladimír Pejchal ◽  
Radovan Vítek ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Molecular Complexes ◽  
Monomeric Unit ◽  
Hydroxyl Groups ◽  
Carboxylic Group ◽  
Chelate Complexes ◽  
119Sn Nmr ◽  
Carboxylic Groups ◽  
Solvent Molecules

The synthesis and structure of tris(1-butyl)tin(IV) and bis(1-butyl)tin(IV) 1-naphthoates, 2-naphthoates, 1-hydroxy-2-naphthoates, 2-hydroxy-1-naphthoates, 3-hydroxy-2-naphthoates as well as the groups of the corresponding tetrakis(1-butyl)dinaphthoato- and tetrakis(1-butyl)bis(hydroxynaphthoato)distannoxanes have been studied in solutions of both coordinating and noncoordinating solvents by means of infrared and multinuclear (1H, 13C and 119Sn) NMR spectroscopies. In the solutions of noncoordinating solvents, all the tris(1-butyl)tin(IV) compounds are present as isolated monomeric molecules with pseudotetrahedral environment of the central tin atom, or as strongly deformed cis-trigonally bipyramidal chelate complexes with anisobidentate carboxylic group. The bis(1-butyl)tin(IV) compounds form molecular pseudooctahedral complexes with chelate anisobidentate carboxylic groups of naphthoate or hydroxynaphthoate ligands. The (1-butyl)chlorotin(IV) compounds are molecular complexes containing a chelate-bound carboxylic group, their tin atom having a pentacoordinated environment of the bond partners. The tetrakis(1-butyl)dinaphthoato- and tetrakis(1-butyl)bis(hydroxynaphthoato)distannoxanes form dimeric molecular complexes with two pentacoordinated tin atoms and two hexacoordinated ones. In solutions of a coordinating solvent (hexadeuteriodimethyl sulfoxide), the tris(1-butyl)tin(IV) compounds form trans-trigonally bipyramidal complexes with one molecule of the solvent, whereas the bis(1-butyl)tin(IV) and bis(1-butyl)chlorotin(IV) compounds form trapezoidally bipyramidal complexes with two molecules of the solvent. The dimeric tetrakis(1-butyl)bis(hydroxynaphthoato)distannoxanes are monomerized by coordinating solvent, each monomeric unit adding two solvent molecules per one tin atom. The environment of the tin atom is then pseudooctahedral. The hydroxyl groups of naphthoate systems do not take part in any bonds to the tin atom in any of the compounds studied.

119Sn, 13C and 1H NMR Spectra of Tris(1-butyl)stannyl D-Glucuronate

1997 ◽  
Vol 62 (8) ◽  
pp. 1169-1176 ◽  
Author(s):  
Antonín Lyčka ◽  
Jaroslav Holeček ◽  
David Micák
Keyword(s):  
Chemical Shift ◽  
Carbonyl Group ◽  
1H Nmr ◽  
Equatorial Plane ◽  
Title Compound ◽  
Nmr Spectra ◽  
Hydroxyl Groups ◽  
Carboxylic Group ◽  
H Nmr ◽  
Oxygen Atoms

The 119Sn, 13C and 1H NMR spectra of tris(1-butyl)stannyl D-glucuronate have been measured in hexadeuteriodimethyl sulfoxide, tetradeuteriomethanol and deuteriochloroform. The chemical shift values have been assigned unambiguously with the help of H,H-COSY, TOCSY, H,C-COSY and 1H-13C HMQC-RELAY. From the analysis of parameters of 119Sn, 13C and 1H NMR spectra of the title compound and their comparison with the corresponding spectra of tris(1-butyl)stannyl acetate and other carboxylates it follows that in solutions of non-coordinating solvents (deuteriochloroform) the title compound is present in the form of more or less isolated individual molecules with pseudotetrahedral environment around the central tin atom and with monodentately bound carboxylic group. The interaction of tin atom with oxygen atoms of carbonyl group and hydroxyl groups of the saccharide residue - if they are present at all - are very weak. In solutions in coordinating solvents (hexadeuteriodimethyl sulfoxide or tetradeuteriomethanol), the title compound forms complexes with one molecule of the solvent. Particles of these complexes have a shape of trigonal bipyramid with the 1-butyl substituents in equatorial plane and the oxygen atoms of monodentate carboxylic group and coordinating solvent in axial positions.

IR and 13C, 17O, and 119Sn NMR spectra of some bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids

1991 ◽  
Vol 56 (9) ◽  
pp. 1908-1915 ◽  
Author(s):  
Jaroslav Holeček ◽  
Antonín Lyčka ◽  
Milan Nádvorník ◽  
Karel Handlíř
Keyword(s):  
Infrared Spectroscopy ◽  
Nmr Spectroscopy ◽  
Dicarboxylic Acid ◽  
Nmr Spectra ◽  
Dicarboxylic Acids ◽  
119Sn Nmr ◽  
Carboxylic Groups ◽  
Cyclic Oligomers ◽  
The Media ◽  
Oxygen Atoms

Infrared spectroscopy and multinuclear (13C, 17O, and 119Sn NMR spectroscopy have been used to study the structure of bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids (1-C4H9)2. Sn(X(COO)2), where X = (CH2)n (n = 0-8), CH=CH (cis and trans) and C6H4 (ortho and para).The crystalline compounds are formed by linear or cyclic oligomers or polymers whose basic building units represent a grouping composed of the central tin atom substituted by two 1-butyl groups and coordinated with both oxygen atoms of two anisobidentate carboxylic groups derived from different molecules of a dicarboxylic acid. The environment of the tin atom has a shape of a trapezoidal bipyramid. When dissolvet in non-coordinating solvents, the compounds retain the oligomeric character with unchanged structure of environment of the central tin atom. In the media of coordinating solvents the bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids form complexes whose central hexacoordinated tin atom binds two molecules of the solvent trough their donor atoms. Carboxylic groups form monodenate linkages in these complexes.

scholarly journals Supramolecular architectures of 4-hydroxytetraphenylporphyrin with aza-donors

2014 ◽  
Vol 70 (a1) ◽  
pp. C554-C554 ◽  
Author(s):  
Purnendu Nandy ◽  
V. Pedireddi
Keyword(s):  
Three Dimensional ◽  
Molecular Complexes ◽  
Hydroxyl Groups ◽  
X Ray Diffraction ◽  
X Ray ◽  
Supramolecular Architectures ◽  
Detailed Structural Analysis ◽  
Different Types ◽  
Solvent Molecules ◽  
Molecular Adducts

Molecular adducts of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1) with aza-donors like 4,4'-bipyridine (a), 1,2-bis(4-pyridyl)ethane (b), trans-1,2-bis(4-pyridyl)ethylene (c), 4,4'-trimethylene-dipyridine (d), phenazine (e), 1,10-phenanthroline (f), 1,7-phenanthroline (g) and 4,7-phenanthroline (h) have been prepared. All the molecular complexes are crystallized along with the solvent of crystallization, except in the complex with the aza-donor b. Detailed structural analysis of the obtained complexes has been carried out by single crystal X-ray diffraction. The three dimensional structures of the molecular adducts are facilitated by directional hydrogen bonding features of hydroxyl groups with aza donors as well as solvent molecules, leading to the formation of different types of supramolecular architectures like sheets, tapes, host-guest assembly etc. For example, in the complex of 1 and aza donor a, which crystallizes as a hydrate, the porphyrin molecules interact with water and 4,4'-bipyridine through O-H...O and O-H...N hydrogen bonds, which leads to the formation of molecular sheets in two dimensional arrangement. An important noteworthy observation is that the molecular complexes are crystalline even after removal of the solvents by heating, as characterized by thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Further, all the complexes are found to be fluorescence sensitive, perhaps due to the porphyrin molecules.

scholarly journals Combined Use of Structure Analysis, Studies of Molecular Association in Solution, and Molecular Modelling to Understand the Different Propensities of Dihydroxybenzoic Acids to Form Solid Phases

Pharmaceutics ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 734
Author(s):  
Aija Trimdale ◽  
Anatoly Mishnev ◽  
Agris Bērziņš
Keyword(s):  
Crystal Structure ◽  
Molecular Dynamics ◽  
Molecular Dynamics Simulations ◽  
Structure Analysis ◽  
Crystal Structure Analysis ◽  
Molecular Association ◽  
Hydroxyl Groups ◽  
Solid Phases ◽  
Solvent Molecules ◽  
Dynamics Simulations

The arrangement of hydroxyl groups in the benzene ring has a significant effect on the propensity of dihydroxybenzoic acids (diOHBAs) to form different solid phases when crystallized from solution. All six diOHBAs were categorized into distinctive groups according to the solid phases obtained when crystallized from selected solvents. A combined study using crystal structure and molecule electrostatic potential surface analysis, as well as an exploration of molecular association in solution using spectroscopic methods and molecular dynamics simulations were used to determine the possible mechanism of how the location of the phenolic hydroxyl groups affect the diversity of solid phases formed by the diOHBAs. The crystal structure analysis showed that classical carboxylic acid homodimers and ring-like hydrogen bond motifs consisting of six diOHBA molecules are prominently present in almost all analyzed crystal structures. Both experimental spectroscopic investigations and molecular dynamics simulations indicated that the extent of intramolecular bonding between carboxyl and hydroxyl groups in solution has the most significant impact on the solid phases formed by the diOHBAs. Additionally, the extent of hydrogen bonding with solvent molecules and the mean lifetime of solute–solvent associates formed by diOHBAs and 2-propanol were also investigated.

13C and 119Sn NMR spectra of some tribenzyltin(IV) compounds

1987 ◽  
Vol 333 (3) ◽  
pp. 305-315 ◽  
Author(s):  
A. Lyčka ◽  
J. Jirman ◽  
A. Koloničný ◽  
J. Holeček
Keyword(s):  
Nmr Spectra ◽  
119Sn Nmr

Charge Transfer Molecular Complexes of 4-(Dimethylamino)pyridine with Some Conventional and Unconventional Acceptors Involving Fluoroarenes

2006 ◽  
Vol 71 (9) ◽  
pp. 1359-1370 ◽  
Author(s):  
Usama M. Rabie
Keyword(s):  
Charge Transfer ◽  
Nmr Spectra ◽  
Molecular Complexes ◽  
Outer Sphere ◽  
Formation Constants ◽  
Stoichiometric Ratio ◽  
Spectral Bands ◽  
Elemental Analyses ◽  
Ct Complexes ◽  
Solid Complexes

Charge transfer (CT) complexes of 4-(dimethylamino)pyridine (DMAP) with iodine as a typical σ-type acceptor and with typical π-type acceptor, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), have been synthesized and characterized. Octafluorotoluene (OFT), octafluoronaphthalene (OFN), perfluorophenanthrene (PFP), and 2,3,5,6-tetrafluoropyridine-4-carbonitrile (TFP) were also used as acceptors for interaction with DMAP. Properties of such CT complexes were investigated by UV/VIS and IR spectra, and elemental analyses of the isolated complexes. The systems DMAP-iodine and DMAP-DDQ are characterized by formation of triiodide ions (I3-) and DDQ•- anion radicals, respectively, which is proposed to occur via initial formation of outer-sphere CT complexes. The systems (DMAP-OFT, DMAP-OFN, DMAP-PFP and DMAP-TFP) are characterized by the appearance of new UV/VIS spectral bands assigned as CT bands; they also furnished the corresponding solid complexes with the stoichiometric ratio 1:1. 1H and 19F NMR spectra were used on confirming the formation of the DMAP-PFP CT complexes. The formation constants (KCT) and molar absorption coefficients (εCT) of the latter complex were obtained.

scholarly journals Bis-Tridendate Ir(III) Polymer-Metallocomplexes: Hybrid, Main-Chain Polymer Phosphors for Orange–Red Light Emission

Polymers ◽  
2020 ◽  
Vol 12 (12) ◽  
pp. 2976
Author(s):  
Konstantinos Andrikopoulos ◽  
Charalampos Anastasopoulos ◽  
Joannis K. Kallitsis ◽  
Aikaterini K. Andreopoulou
Keyword(s):  
Main Chain ◽  
Light Emission ◽  
Red Light ◽  
Molecular Complexes ◽  
Hydroxyl Groups ◽  
Iridium Complexes ◽  
Light Emitters ◽  
Chain Polymer ◽  
Molecular Weights ◽  
Pyridine Moiety

In this work, hybrid polymeric bis-tridentate iridium(III) complexes bearing derivatives of terpyridine (tpy) and 2,6-di(phenyl) pyridine as ligands were successfully synthesized and evaluated as red-light emitters. At first, the synthesis of small molecular bis-tridendate Ir(III) complexes bearing alkoxy-, methyl-, or hydroxy-functionalized terpyridines and a dihydroxyphenyl-pyridine moiety was accomplished. Molecular complexes bearing two polymerizable end-hydroxyl groups and methyl- or alkoxy-decorated terpyridines were copolymerized with difluorodiphenyl-sulphone under high temperature polyetherification conditions. Alternatively, the post-polymerization complexation of the terpyridine-iridium(III) monocomplexes onto the biphenyl-pyridine main chain homopolymer was explored. Both cases afforded solution-processable metallocomplex-polymers possessing the advantages of phosphorescent emitters in addition to high molecular weights and excellent film-forming ability via solution casting. The structural, optical, and electrochemical properties of the monomeric and polymeric heteroleptic iridium complexes were thoroughly investigated. The polymeric metallocomplexes were found to emit in the orange–red region (550–600 nm) with appropriate HOMO and LUMO levels to be used in conjunction with blue-emitting hosts. By varying the metal loading on the polymeric backbone, the emitter’s specific emission maxima could be successfully tuned.

Koordinationschemie π-gebundener Cyclopentadienyl-Chalcogeno-Ether, II. Palladium(II)- und Platin(II)-Komplexe von [C5(SMe)5]Mn(CO)3, [C5Cl2(SMe)3]Mn(CO)3 und [C5Cl2(SMe)2(PPh2)]Mn(CO)3./ Coordination Chemistry of π-Bonded Cyclopentadienyl Chalcogeno Ethers, II. Palladium(II) and Platinum(II) Complexes of [C5(SMe)5]Mn(CO)3, [C5Cl2(SMe)3]Mn(CO)3 and [C5Cl2(SMe)2(PPh2)]Mn(CO)3

1995 ◽  
Vol 50 (9) ◽  
pp. 1307-1318 ◽  
Author(s):  
Karlheinz Sünkel ◽  
Adrian Blum
Keyword(s):  
Coordination Chemistry ◽  
Crystal Structures ◽  
Nmr Spectra ◽  
Chelate Complexes ◽  
H Nmr ◽  
Pt Complex ◽  
Meso Form

AbstractTreatment of the cymantrene thioether [C5(SMe)5]Mn(CO)3 (IIb) with Na2PdCl4 or K2PtCl4 yields the bimetallic chelate complexes [C5(SMe)5]Mn(CO)3*MCl2 (M = Pd (2) or Pt (3)). Similarly, the S,P-chelate complexes [C5Cl2(SR)2(PPh2)]Mn(CO)3*PdCl2 (R = Me (4a), Ph (4b)) can be obtained from the corresponding mononuclear cymantrene derivatives and Na2PdCl4 or (PhCN)2PdCl2. Analysis of the 1H NMR spectra only allows for the Pt complex the identification of one meso form, which seems to be favoured by 2:1, together with the D,L forms. The crystal structures of [C5Cl2(SMe)3]Mn(CO)3*PdCl2(1, C11H9Cl4MnO3PdS3, triclinic, P1̄, a = 7.617(3) Å , b = 10.528(4) Å ,c = 12.473(5) Å , α = 72.95(3)°, β = 84.94(3)°, γ = 88.75(3)°, V = 952.6(6) Å3, Z = 2), 2 (C13H15Cl2MnO3PdS5, orthorhombic, Pn21/c, a = 12.739(5) Å , b = 9.992(3) Å , c = 16.884(5) Å , V = 2149(1) Å, Z = 4), and 4 (C23H18Cl6MnO3PPdS2, monoclinic, P21/c, a = 13.199(4) Å , b = 29.198(11) Å , c = 15.921(7) , β - 101.41(3)°, V = 6015(4) Å3, Z = 8) are reported and compared with each other and other bimetallic metallocene phosphine and thioether derivatives.

Phosphinsubstituierte Chelatliganden, XIV [1]. Wasserstoff-Brückenbindung in THF-Addukten von Tetracarbonylchrom-und -molybdänkomplexen mit P,S-koordinierten Phosphinothioformamid-Liganden. Kristallstruktur von [(CO)4Cr(PPh2C(S)NHMe)] · THF Phosphine-Substituted Chelate Ligands, XIV [1]. Hydrogen Bonding in THF-Adducts of Tetracarbonylchromium and -molybdenum Complexes with P,S-Coordinated Phosphinothioformamide Ligands. Crystal Structure of [(CO)4Cr(PPh2C(S)NHMe)] · THF

1985 ◽  
Vol 40 (4) ◽  
pp. 512-517 ◽  
Author(s):  
Udo Kunze ◽  
Hussain Jawad ◽  
Wolfgang Hiller ◽  
Regina Naumer
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Nmr Spectra ◽  
Chelate Complexes ◽  
Triclinic Space Group ◽  
Lattice Constants ◽  
H Nmr ◽  
Contact Distance ◽  
Metal Hexacarbonyls

The tetracarbonyl chromium and molybdenum P,S-chelate complexes 1a, b and 2a, b are obtained by low-temperature photolysis of the metal hexacarbonyls with the neutral phosphinothioformamide ligands, Ph2PC(S)NHR (R = Me (a). Ph (b)), as stoichiometric 1/1 IHF adducts. A weak N-H···O(THF) hydrogen bond is deduced from the 1H NMR spectra which show a collapse of the N-methyl doublet in la (Tc -18 °C) but not in 2a. Unusually small P-C(S) couplings are observed in the 13C{1H} NMR spectra. The N-methyl chromium complex la crystal­lizes in the triclinic space group P1 (Z = 2) with the lattice constants a = 1076.6(3), b = 1235.8(3), c = 915.1(3) pm, α = 97.99(4)°, β = 92.73(5)°, γ = 87.63(5)°. The planar thioamide unit adopts the Z configuration and is linked to the tetrahydrofuran molecule by a hydrogen bond (N-H1-O31 164°) with an O···H contact distance of 191 pm.

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