Markku Sundberg - Academia.edu (original) (raw)
Papers by Markku Sundberg
Unknown host publication, 2008
Inorganica Chimica Acta, Dec 1, 1985
Abstract The structure of the title compound was re-determined by X-ray methods and the refinemen... more Abstract The structure of the title compound was re-determined by X-ray methods and the refinement improved from the earlier R value of 0.119 [12] to the value of 0.042. The new cell constants are a = 11.498(2), b = 8.295(2), c = 11.383(2) A, β = 91.84 (1). The symmetry around the Cu(II) ion is near to D4h. The greatest deviation from the symmetry approximated is the tilting of 4.4° of the axial CuO bond from the normal perpendicular to the equatorial CuN4 plane. Another deviation is the endocyclic NCuN angle, which is here 87.09(14)°. Broadening of the v(NH) vibrations and their shifting to lower energies in the IR spectrum are indicative of a hydrogen bonding network (which runs diagonally along the bc plane. The axial bond length CuO is statistically short, 2.468(3) A, and consequently the tetragonality T is rather high, 0.825. The two CO bond lengths in the carboxyate group do not differ significantly: 1.261(5) and 1.247(5) A. Electron population analysis, performed by using CNDO, reveals uneven electron distribution on the carboxylic oxygen atoms and slight polarization between the carboxylic group and the aromatic ring, where the electronic charge is evenly distributed. The UV-Vis spectrum shows bands at 580 and 860 (sh) nm. The band at 860 nm may be assigned either to the d-d transition B1g → A1g (although this is an unusually high wavelength compared with values obtained for similar compounds), or to a charge transfer between the neighbouring benzoate anions.
Inorganica Chimica Acta, Mar 1, 2012
The available experimental structures containing a dichromate dianion were gathered from the ICSD... more The available experimental structures containing a dichromate dianion were gathered from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases. The geometrical parameters show considerably wide range in bond lengths and bond angles. The Cr-O-Cr angle varies between 116.2°and 162.1°. The range for the Cr-O(terminal) bond lengths is between 1.469 and 1.777 Å. The respective range for the Cr-O(bridging) is 1.622-1.956 Å. The dichromate dianion shows also propensity to experience phase transitions in the solid state. The variation in the bonding parameters is likely due to combination of weak bonding and intermolecular interactions. The most common point group is C 1 for a dichromate dianion in the solid state.
Journal of the American Chemical Society, Aug 4, 2000
Journal of Molecular Structure, May 1, 2011
A series of tert-butyl substituted salicylaldimines was synthesized and characterized by IR, 1 H ... more A series of tert-butyl substituted salicylaldimines was synthesized and characterized by IR, 1 H NMR, 13 C NMR, UV-vis, X-ray diffraction and elemental analyses to investigate the effect of two bulky tert-butyl groups on the keto-enol tautomerization in solution and solid state. According to X-ray studies all salicylaldimines have an enol tautomeric form in solid state and due to strong O-HÁÁÁN hydrogen bonding they form a nearly planar intramolecular six-membered ring. Based on NMR, IR and UV-vis studies, the enol form is also present in solutions. Computational studies carried out by the density function theory (DFT) method verifies that in each sterically hindered keto-enol pair the enol form is more stable, although the differences in energy vary from 5.5 to 10.1 kJ/mol (in terms of total energy obtained from Gaussian for the optimized moieties). For the tert-butyl substituted salicylaldimines, solvatochromism is not observed in polar hydrogen bonding solvents. As N-alkyl and N-alkylphenyl substituted salicylaldimines without tert-butyl groups have a solvatochromic band, the sterically bulky tert-butyl groups seem to have a key role in stabilizing the intramolecular hydrogen bonding.
Inorganica Chimica Acta, Nov 1, 2002
The reaction of an ethanolic solutions of N-salicylideneglycinatoaquacopper(II) hemihydrate with ... more The reaction of an ethanolic solutions of N-salicylideneglycinatoaquacopper(II) hemihydrate with urea, pyridine, 2,4dimethylpyridine, 3,5-dimethylpyridine, quinoline, 4-methylquinoline, isoquinoline, or 3-methylisoquinoline in an equimolar ratio resulted in solid products containing complexes of the type Cu(salgly)L with distorted square pyramidal coordination polyhedra. The products were characterized by elemental analysis, electronic and EPR spectra, and magnetic susceptibility measurements. Moreover, the crystal and molecular structure of N-salicylideneglycinatoureacopper(II) dimer was determined by single crystal Xray diffraction methods. The copper(II) atoms are bridged by two phenolic oxygen atoms with a Cu Ã/Cu distance of 3.1093(11) Å and Cu Ã/O Ã/Cu angle of 94.47(12)8. The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi.
Journal of The Chemical Society, Chemical Communications, 1991
American Mineralogist, Feb 1, 1987
Quick Search: All GSW Journals, GSW + GeoRef. advanced search. ...
We study the ammonia addition reactions of H 2 SO 4 •NH 3 molecular clusters containing up to fou... more We study the ammonia addition reactions of H 2 SO 4 •NH 3 molecular clusters containing up to four ammonia and two sulfuric acid molecules using the ab initio method RI-MP2 (Resolution of Identity 2nd order Møller-Plesset perturbation theory). Together with results from previous studies, we use the computed values to estimate an upper limit for the ammonia content of small atmospheric clusters, without having to explicitly include water molecules in the quantum chemical simulations. Our results indicate that the NH 3 :H 2 SO 4 mole ratio of small molecular clusters in typical atmospheric conditions is probably around 1:2. High ammonia concentrations or low temperatures may lead to the formation of ammonium bisulfate (1:1) clusters, but our results rule out the formation of ammonium sulfate clusters (2:1) anywhere in the atmosphere. A sensitivity analysis indicates that the qualitative conclusions of this study are not affected even by relatively large errors in the calculation of electronic energies or vibrational frequencies.
ChemInform, Jan 23, 1990
ChemInform Abstract Solid state 13C CP MAS and solution 13C, 15N, 14N, and 17O NMR spectra are me... more ChemInform Abstract Solid state 13C CP MAS and solution 13C, 15N, 14N, and 17O NMR spectra are measured for (I)-(III); (II) has space group P21/m with Z=2 and (III) has Pbca with Z = 8.
Journal of the American Society for Mass Spectrometry, Jun 1, 1995
A study was carried out on the fragmentation of 12 protonated O,O-dimethyl 0-aryl phosphorothiona... more A study was carried out on the fragmentation of 12 protonated O,O-dimethyl 0-aryl phosphorothionates by tandem quadrupole mass spectrometry. Some of the studied compounds are used in agriculture as pesticides. Energy-resolved and pressure-resolved experiments were performed on the [M + HI+ ions to investigate the dissociation behavior of the ions with various amounts of internal energy. On collisionally activated dissociation, the [M + HI+ ions decompose to yield the [M + H-CHsOHl+, (CH,O),PS+ (m/z 1251, and (CH,O),PO+ (m/z 109) ions as major fragments. The ions [M + H-CH,OH]+ and (CHs0)2PS+ probably arise from the [M + HI" ions of the 0,0-dimethyl 0-aryl phospho rothionates with the proton on the sulfur or on the oxygen of the phenoxy group. The origin of the hydroxy proton of the methanol fragment was in many cases, surprisingly, the phenyl group and not the reagent gas. This was confirmed by using deuterated isobutane, C4D10, as reagent gas in Cl. The fragment ions (CH30)2PO+ and [ZPhS]+ are the results of thiono-thiolo rearrangement reaction. The precursor ion for the ion (CH30)rPO+ arises from most compounds upon chemical ionization, whereas the precursor ion for the ion [ZPhS]+ arises only from a few compounds upon chemical ionization. The observed fragments imply that several sites carry the extra proton and that these sites get the proton usually upon ionization. The stability order and some characteristics of three protomers of 0,0-dimethyl 0-phenyl phosphorothionate were investigated by ab initio calculations at the RHF/3-21G* level of theory.
Journal of Physical Chemistry A, Aug 18, 1998
ABSTRACT
Journal of the Chemical Society, 1989
Page 1. J. CHEM. SOC. PERKIN TRANS. II 1989 1397 NMR Spectroscopic and X-Ray Crystallographic Stu... more Page 1. J. CHEM. SOC. PERKIN TRANS. II 1989 1397 NMR Spectroscopic and X-Ray Crystallographic Studies on some o-NO, Substituted Aromatic Sulphur Amides Pirkko Ruostesuo * Department of Chemistry, University of ...
Inorganica Chimica Acta, Nov 1, 2001
The crystal and molecular structure of trans-di(ortho-hydroxobenzoato-O)bis(1,3-diaminopropane-N,... more The crystal and molecular structure of trans-di(ortho-hydroxobenzoato-O)bis(1,3-diaminopropane-N,N′)copper(II) [ortho-hydroxobenzoate=salicylate hereafter] determined by single crystal X-ray diffraction methods at T=193(2) K. The structure is composed of monomeric complex units with the central copper(II) ion occupying a centre of symmetry. The coordination polyhedron can be described as axially elongated distorted octahedron with the axial Cu–O bond length of 2.559(3) Å indicating semi-coordination. There is notable asymmetry in the coordinated 1,3-diaminopropane molecule, which forms a six-membered chelate ring displaying Cu–N1–C1 and Cu–N2–C3 angles of 121.5(2) and 117.4(2)°, respectively. This deviation may be correlated to differences in hydrogen bonding between the amino groups and the non-coordinated oxygen atoms of the salicylate anions. The coordinated salicylate anion shows considerable declination of 28.9°, which may be correlated to intramolecular hydrogen bonding. The electronic properties of benzoate anions were studied by Natural Bond Order (NBO) analyses for optimised model compounds at the MP2/6-311+G*//MP2/6-311+G* level of theory. The results suggest that semi-coordination is mainly characterised by concomitant electrostatic attraction of the charges at the central copper(II) cation and repulsion between an electron lone pair of a ligand atom and the electron lone pair at the copper(II) 3dz2 atomic orbital.
Inorganica Chimica Acta, Apr 1, 1995
Conformational isomerism and effect of complexation on carboxylate group in two crystallographica... more Conformational isomerism and effect of complexation on carboxylate group in two crystallographically independent coordination units of trans-di(4-chlorobenzoato-O)bis(1,3diaminopropane-N,N')cobalt(III) 4-chlorobenzoate dihydrate
Polyhedron, Apr 1, 1996
survey of 123 of copper(I1) acetate-type dimeric complex units, determined by X-ray diffraction i... more survey of 123 of copper(I1) acetate-type dimeric complex units, determined by X-ray diffraction in the crystal structures containing either a CuO,O or CuO,N chromophore, gave the following results. All the distorted square pyramidal coordination spheres contain a copper atom displaced 0.16550.225 and 0.1840.322 A from the basal 0, plane in CuO,O and Cu04N chromophores, respectively. The Cu-Cu distances were in the range of 2.575-2.702 and 2.60332.886 A for the CuO,O and Cu04N chromophores. respectively. The apical ligand atoms show large coefficients of variation for the distortion from the perpendicular to the basal 0, plane. There is highly significant propensity for the copper atoms to move out from the basal 0, plane upon elongation of the Cu-Cu distance. Strong negative correlations were found between the Cu-O-C and O-CO angles. The most marked deviations for the observed parameters are caused by the bridges containing a halogenoacetate anion, leading to distorted trigonal bipyramidal geometry.
Acta Chemica Scandinavica, 1981
Inorganica Chimica Acta, Sep 1, 1987
ABSTRACT
ChemInform, Aug 19, 2010
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Unknown host publication, 2008
Inorganica Chimica Acta, Dec 1, 1985
Abstract The structure of the title compound was re-determined by X-ray methods and the refinemen... more Abstract The structure of the title compound was re-determined by X-ray methods and the refinement improved from the earlier R value of 0.119 [12] to the value of 0.042. The new cell constants are a = 11.498(2), b = 8.295(2), c = 11.383(2) A, β = 91.84 (1). The symmetry around the Cu(II) ion is near to D4h. The greatest deviation from the symmetry approximated is the tilting of 4.4° of the axial CuO bond from the normal perpendicular to the equatorial CuN4 plane. Another deviation is the endocyclic NCuN angle, which is here 87.09(14)°. Broadening of the v(NH) vibrations and their shifting to lower energies in the IR spectrum are indicative of a hydrogen bonding network (which runs diagonally along the bc plane. The axial bond length CuO is statistically short, 2.468(3) A, and consequently the tetragonality T is rather high, 0.825. The two CO bond lengths in the carboxyate group do not differ significantly: 1.261(5) and 1.247(5) A. Electron population analysis, performed by using CNDO, reveals uneven electron distribution on the carboxylic oxygen atoms and slight polarization between the carboxylic group and the aromatic ring, where the electronic charge is evenly distributed. The UV-Vis spectrum shows bands at 580 and 860 (sh) nm. The band at 860 nm may be assigned either to the d-d transition B1g → A1g (although this is an unusually high wavelength compared with values obtained for similar compounds), or to a charge transfer between the neighbouring benzoate anions.
Inorganica Chimica Acta, Mar 1, 2012
The available experimental structures containing a dichromate dianion were gathered from the ICSD... more The available experimental structures containing a dichromate dianion were gathered from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases. The geometrical parameters show considerably wide range in bond lengths and bond angles. The Cr-O-Cr angle varies between 116.2°and 162.1°. The range for the Cr-O(terminal) bond lengths is between 1.469 and 1.777 Å. The respective range for the Cr-O(bridging) is 1.622-1.956 Å. The dichromate dianion shows also propensity to experience phase transitions in the solid state. The variation in the bonding parameters is likely due to combination of weak bonding and intermolecular interactions. The most common point group is C 1 for a dichromate dianion in the solid state.
Journal of the American Chemical Society, Aug 4, 2000
Journal of Molecular Structure, May 1, 2011
A series of tert-butyl substituted salicylaldimines was synthesized and characterized by IR, 1 H ... more A series of tert-butyl substituted salicylaldimines was synthesized and characterized by IR, 1 H NMR, 13 C NMR, UV-vis, X-ray diffraction and elemental analyses to investigate the effect of two bulky tert-butyl groups on the keto-enol tautomerization in solution and solid state. According to X-ray studies all salicylaldimines have an enol tautomeric form in solid state and due to strong O-HÁÁÁN hydrogen bonding they form a nearly planar intramolecular six-membered ring. Based on NMR, IR and UV-vis studies, the enol form is also present in solutions. Computational studies carried out by the density function theory (DFT) method verifies that in each sterically hindered keto-enol pair the enol form is more stable, although the differences in energy vary from 5.5 to 10.1 kJ/mol (in terms of total energy obtained from Gaussian for the optimized moieties). For the tert-butyl substituted salicylaldimines, solvatochromism is not observed in polar hydrogen bonding solvents. As N-alkyl and N-alkylphenyl substituted salicylaldimines without tert-butyl groups have a solvatochromic band, the sterically bulky tert-butyl groups seem to have a key role in stabilizing the intramolecular hydrogen bonding.
Inorganica Chimica Acta, Nov 1, 2002
The reaction of an ethanolic solutions of N-salicylideneglycinatoaquacopper(II) hemihydrate with ... more The reaction of an ethanolic solutions of N-salicylideneglycinatoaquacopper(II) hemihydrate with urea, pyridine, 2,4dimethylpyridine, 3,5-dimethylpyridine, quinoline, 4-methylquinoline, isoquinoline, or 3-methylisoquinoline in an equimolar ratio resulted in solid products containing complexes of the type Cu(salgly)L with distorted square pyramidal coordination polyhedra. The products were characterized by elemental analysis, electronic and EPR spectra, and magnetic susceptibility measurements. Moreover, the crystal and molecular structure of N-salicylideneglycinatoureacopper(II) dimer was determined by single crystal Xray diffraction methods. The copper(II) atoms are bridged by two phenolic oxygen atoms with a Cu Ã/Cu distance of 3.1093(11) Å and Cu Ã/O Ã/Cu angle of 94.47(12)8. The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi.
Journal of The Chemical Society, Chemical Communications, 1991
American Mineralogist, Feb 1, 1987
Quick Search: All GSW Journals, GSW + GeoRef. advanced search. ...
We study the ammonia addition reactions of H 2 SO 4 •NH 3 molecular clusters containing up to fou... more We study the ammonia addition reactions of H 2 SO 4 •NH 3 molecular clusters containing up to four ammonia and two sulfuric acid molecules using the ab initio method RI-MP2 (Resolution of Identity 2nd order Møller-Plesset perturbation theory). Together with results from previous studies, we use the computed values to estimate an upper limit for the ammonia content of small atmospheric clusters, without having to explicitly include water molecules in the quantum chemical simulations. Our results indicate that the NH 3 :H 2 SO 4 mole ratio of small molecular clusters in typical atmospheric conditions is probably around 1:2. High ammonia concentrations or low temperatures may lead to the formation of ammonium bisulfate (1:1) clusters, but our results rule out the formation of ammonium sulfate clusters (2:1) anywhere in the atmosphere. A sensitivity analysis indicates that the qualitative conclusions of this study are not affected even by relatively large errors in the calculation of electronic energies or vibrational frequencies.
ChemInform, Jan 23, 1990
ChemInform Abstract Solid state 13C CP MAS and solution 13C, 15N, 14N, and 17O NMR spectra are me... more ChemInform Abstract Solid state 13C CP MAS and solution 13C, 15N, 14N, and 17O NMR spectra are measured for (I)-(III); (II) has space group P21/m with Z=2 and (III) has Pbca with Z = 8.
Journal of the American Society for Mass Spectrometry, Jun 1, 1995
A study was carried out on the fragmentation of 12 protonated O,O-dimethyl 0-aryl phosphorothiona... more A study was carried out on the fragmentation of 12 protonated O,O-dimethyl 0-aryl phosphorothionates by tandem quadrupole mass spectrometry. Some of the studied compounds are used in agriculture as pesticides. Energy-resolved and pressure-resolved experiments were performed on the [M + HI+ ions to investigate the dissociation behavior of the ions with various amounts of internal energy. On collisionally activated dissociation, the [M + HI+ ions decompose to yield the [M + H-CHsOHl+, (CH,O),PS+ (m/z 1251, and (CH,O),PO+ (m/z 109) ions as major fragments. The ions [M + H-CH,OH]+ and (CHs0)2PS+ probably arise from the [M + HI" ions of the 0,0-dimethyl 0-aryl phospho rothionates with the proton on the sulfur or on the oxygen of the phenoxy group. The origin of the hydroxy proton of the methanol fragment was in many cases, surprisingly, the phenyl group and not the reagent gas. This was confirmed by using deuterated isobutane, C4D10, as reagent gas in Cl. The fragment ions (CH30)2PO+ and [ZPhS]+ are the results of thiono-thiolo rearrangement reaction. The precursor ion for the ion (CH30)rPO+ arises from most compounds upon chemical ionization, whereas the precursor ion for the ion [ZPhS]+ arises only from a few compounds upon chemical ionization. The observed fragments imply that several sites carry the extra proton and that these sites get the proton usually upon ionization. The stability order and some characteristics of three protomers of 0,0-dimethyl 0-phenyl phosphorothionate were investigated by ab initio calculations at the RHF/3-21G* level of theory.
Journal of Physical Chemistry A, Aug 18, 1998
ABSTRACT
Journal of the Chemical Society, 1989
Page 1. J. CHEM. SOC. PERKIN TRANS. II 1989 1397 NMR Spectroscopic and X-Ray Crystallographic Stu... more Page 1. J. CHEM. SOC. PERKIN TRANS. II 1989 1397 NMR Spectroscopic and X-Ray Crystallographic Studies on some o-NO, Substituted Aromatic Sulphur Amides Pirkko Ruostesuo * Department of Chemistry, University of ...
Inorganica Chimica Acta, Nov 1, 2001
The crystal and molecular structure of trans-di(ortho-hydroxobenzoato-O)bis(1,3-diaminopropane-N,... more The crystal and molecular structure of trans-di(ortho-hydroxobenzoato-O)bis(1,3-diaminopropane-N,N′)copper(II) [ortho-hydroxobenzoate=salicylate hereafter] determined by single crystal X-ray diffraction methods at T=193(2) K. The structure is composed of monomeric complex units with the central copper(II) ion occupying a centre of symmetry. The coordination polyhedron can be described as axially elongated distorted octahedron with the axial Cu–O bond length of 2.559(3) Å indicating semi-coordination. There is notable asymmetry in the coordinated 1,3-diaminopropane molecule, which forms a six-membered chelate ring displaying Cu–N1–C1 and Cu–N2–C3 angles of 121.5(2) and 117.4(2)°, respectively. This deviation may be correlated to differences in hydrogen bonding between the amino groups and the non-coordinated oxygen atoms of the salicylate anions. The coordinated salicylate anion shows considerable declination of 28.9°, which may be correlated to intramolecular hydrogen bonding. The electronic properties of benzoate anions were studied by Natural Bond Order (NBO) analyses for optimised model compounds at the MP2/6-311+G*//MP2/6-311+G* level of theory. The results suggest that semi-coordination is mainly characterised by concomitant electrostatic attraction of the charges at the central copper(II) cation and repulsion between an electron lone pair of a ligand atom and the electron lone pair at the copper(II) 3dz2 atomic orbital.
Inorganica Chimica Acta, Apr 1, 1995
Conformational isomerism and effect of complexation on carboxylate group in two crystallographica... more Conformational isomerism and effect of complexation on carboxylate group in two crystallographically independent coordination units of trans-di(4-chlorobenzoato-O)bis(1,3diaminopropane-N,N')cobalt(III) 4-chlorobenzoate dihydrate
Polyhedron, Apr 1, 1996
survey of 123 of copper(I1) acetate-type dimeric complex units, determined by X-ray diffraction i... more survey of 123 of copper(I1) acetate-type dimeric complex units, determined by X-ray diffraction in the crystal structures containing either a CuO,O or CuO,N chromophore, gave the following results. All the distorted square pyramidal coordination spheres contain a copper atom displaced 0.16550.225 and 0.1840.322 A from the basal 0, plane in CuO,O and Cu04N chromophores, respectively. The Cu-Cu distances were in the range of 2.575-2.702 and 2.60332.886 A for the CuO,O and Cu04N chromophores. respectively. The apical ligand atoms show large coefficients of variation for the distortion from the perpendicular to the basal 0, plane. There is highly significant propensity for the copper atoms to move out from the basal 0, plane upon elongation of the Cu-Cu distance. Strong negative correlations were found between the Cu-O-C and O-CO angles. The most marked deviations for the observed parameters are caused by the bridges containing a halogenoacetate anion, leading to distorted trigonal bipyramidal geometry.
Acta Chemica Scandinavica, 1981
Inorganica Chimica Acta, Sep 1, 1987
ABSTRACT
ChemInform, Aug 19, 2010
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.