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Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests

  • Inge Warttmann and Günter Häfelinger
Published/Copyright: June 2, 2014
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 10

Abstract

Ab initio Hartree-Fock (HF) and density functional (DFT) optimizations on the test m olecule osmiumtetracarbonyldihydride (13) with various basis sets show that the lanl2mb pseudopotential basis set for osmium leads in the HF approximation to more reliable molecular geometries than the DFT calculations. This HF procedure was used for the optimizations of molecular geometries of three isomeric 4,4,4,4,17,17,17,17-octacarbonyl-4,17-diosma[7.7]ortho-, meta- and paracyclophanes 1 to 3, of which 3 was found to be predestined for formation of various host-guest complexes with possible guests benzene (4), fluorobenzene (5), 1,3,5- trifluorobenzene (6), 1,2,4,5-tetrafluorobenzene (7), hexafluorobenzene (8), fluoroanil (9), tetrafluoroethene (10), tetracyanoethene (11) and aniline (12). Results of optimized hostguest geometries are presented graphically for inclusions and associations of guest 4 to 12 with 3. Calculated lanl2mb interaction energies, after correction for basis set superposition error (BSSE), remain favourable only for inclusion of 5 and associations of 5, 10, 11 and 12. Additionally lanl2dz single point calculations for inclusion, which may not need BSSE correction because of the improved basis set, are favourable for 6 and 12. According to lanl2mb HOMO and LUMO energies, 3 may as well easily donate or accept electrons. This may be an interpretation to the surprising effect, that Mulliken total charges are positive on the electron accepting guest molecules 4 to 11. There are geometrical peculiarities in the optimized host-guest complexes for inclusion and association. Fluorine atoms of 5 to 10 and nitrogen atoms of a cyano group of 11 and the amino group of 12 like to come close to one or two carbonyl groups. Similar distances of 2.70 Å to 3.57 Å between the O atom of the carbonyl group and the F atom or N atom appear in all optimizations of inclusion and association of 5 to 12 except in the case of association of tetrafluoroethene (10).

Keywords: Geometry Optimizations; Osmiumtetracarbonyldihydride; Bis-Osmium-Metallacyclophanes; Host-Guest Complexes; Tetrafluoroethene
Received: 1998-7-22
Published Online: 2014-6-2
Published in Print: 1998-10-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation
  2. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2 Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2 Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur
  3. Phosphenium-Komplexe, 43 [1]. Ringöffnungsreaktionen der dreigliedrigen Phosphametallacyclen {PR2 = P(o-Tol)2, P(Ph)(o-Tol), P(Mes)[C(S)N(H)Et], P(/-Bu)[C(O)N(H)Et} / Phosphenium Complexes, 43 [1]. Ring-Opening Reactions of the Three-Membered Phosphametallacycles {PR1 = P(o-Tol)2, P(Ph)(oTol), P(Mes)[C(S)N(H)Et], P(r-Bu)[C(0)N(H)Et}
  4. Magnesium Bis[D(-)-Mandelate] Dihydrate and Other Alkaline Earth, Alkali, and Zinc Salts of Mandelic Acid
  5. The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation
  6. Kristallchemische Beziehungen von CO6O2 [TeO4 (CoAsO5)2] zur Steinsalzstruktur von CoO mit einem Beitrag über magnetische Messungen an CO6O2[TeO4(CoAsO5)2] / Crystal Chemical Relations of Co6O2[TeO4(CoAsO5)2] to the Rocksalt Structure of CoO and a Contribution on Magnetic Measurements of Co6O2[TeO4(CoAsO5)2]
  7. Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O
  8. Untersuchungen an Polyhalogeniden, XXXVII [1]. Heptaiodide(3-) von Amminkomplexen des Chroms und Cobalts: Hexamminchrom(III)heptaiodid [Cr(NH3)6](I3)(I4) und die Tri-μ-hydroxo-bis[metall(III)-triammin]heptaiodide [(NH3)3 M(OH)3M(NH3)3](I3)2I mit M = Co, Cr / Studies o f Polyhalides, XXXVII [1]. Heptaiodides(3-) of Ammine Complexes of Chromium and Cobalt: Hexamminechromium(III) heptaiodide [Cr(NH3)6](I3)(I4) and the Tri-μ-hydroxo-bis[metal(III)-triammine] heptaiodides [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Co, Cr
  9. Functionalized 1,1-Ethene Dithiolates as Ligands, V [1]. Synthesis and Crystal Structure of Palladium(II) and Platinum(II) Complexes with Dithioylidene Barbituric Acid Ligands. Molecular Structure of a 2,6-Diaminopyridine-Platinum(II) Barbiturate Complex
  10. Solvothermal Synthesis and Crystal Structure Determination of Tris- (ethyleneamine-ammonium) Tetraselenoantimonat: Non-Centrosymmetry Mediated by an Extended Unusual N-H···N Hydrogen Bonded Network?
  11. Thermische Zersetzung und Lösungskalorimetrie von Ammoniumeuropiumchloriden / Thermal Decomposition and Solution Calorimetry of Ammonium Europium Chlorides
  12. Photochemical Reductive Elimination of Nitrogen from Triazidogallium(III). Generation of Luminescent Gallium(I)
  13. Zur Existenz von [ReNCl4-nFn]- (n = 1-3) Nitridorhenat(VI)-Gemischt- ligandkomplexen -Eine EPR-Untersuchung / EPR Evidence of [ReNCl4-n FnJ– (n = 1-3) Nitridorhenate(VI) Mixed-Ligand Complexes
  14. Synthesis and Crystal Structure of N-[(15,4R)-2-Oxo-pinanyl]-β-alanine Methylester
  15. Synthesis and Conformation of Nucleoside 5'-S-Thiosulfates
  16. Niedere Hydrate aliphatischer primärer Amine. Neue Untersuchungen zu Bildung und Struktur [1] / Lower Hydrates of Aliphatic Primary Amines. New Studies of Formation and Structure [1]
  17. Synthesis and Dimroth Rearrangement of 6-Cyano-l,2,4-triazolo- [4,3-a]pyrimidin-5- and 7-ones. A Novel Alkylation with Orthoesters and a New Participation of the Cyano Group in the Rearrangement
  18. Synthesis and Thermal Properties of Twin Compounds, Alkanediacids 4-(4'-Cyano)-biphenyl Diesters
  19. Synthesis of Pyrrolo-, Thienopyrrolo-, Benzothienopyrroloquinolines as well as Triazoloindole Derivatives
  20. Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests
  21. Preparation and Crystal Structure of Cs4Nb2S11
  22. On the Metalation of 2,6-Dimethyl-4-tert-butyl-thiophenol
  23. Kristallstruktur des Oxo-Acetatkomplexes [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] / Crystal Structure of the Oxo-Acetate Complex [Co7(μ4 -O)2(O2CCH3)10(OPEt3)2]
  24. Penol Catalyzed Claisen ortho Ester Rearrangment of Allylic Alcohols with Trimethyl-β-hoxy) ortho Propionate
https://doi.org/10.1515/znb-1998-1020
Keywords for this article
Geometry Optimizations; Osmiumtetracarbonyldihydride; Bis-Osmium-Metallacyclophanes; Host-Guest Complexes; Tetrafluoroethene

Articles in the same Issue

  1. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation
  2. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2 Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2 Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur
  3. Phosphenium-Komplexe, 43 [1]. Ringöffnungsreaktionen der dreigliedrigen Phosphametallacyclen {PR2 = P(o-Tol)2, P(Ph)(o-Tol), P(Mes)[C(S)N(H)Et], P(/-Bu)[C(O)N(H)Et} / Phosphenium Complexes, 43 [1]. Ring-Opening Reactions of the Three-Membered Phosphametallacycles {PR1 = P(o-Tol)2, P(Ph)(oTol), P(Mes)[C(S)N(H)Et], P(r-Bu)[C(0)N(H)Et}
  4. Magnesium Bis[D(-)-Mandelate] Dihydrate and Other Alkaline Earth, Alkali, and Zinc Salts of Mandelic Acid
  5. The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation
  6. Kristallchemische Beziehungen von CO6O2 [TeO4 (CoAsO5)2] zur Steinsalzstruktur von CoO mit einem Beitrag über magnetische Messungen an CO6O2[TeO4(CoAsO5)2] / Crystal Chemical Relations of Co6O2[TeO4(CoAsO5)2] to the Rocksalt Structure of CoO and a Contribution on Magnetic Measurements of Co6O2[TeO4(CoAsO5)2]
  7. Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O
  8. Untersuchungen an Polyhalogeniden, XXXVII [1]. Heptaiodide(3-) von Amminkomplexen des Chroms und Cobalts: Hexamminchrom(III)heptaiodid [Cr(NH3)6](I3)(I4) und die Tri-μ-hydroxo-bis[metall(III)-triammin]heptaiodide [(NH3)3 M(OH)3M(NH3)3](I3)2I mit M = Co, Cr / Studies o f Polyhalides, XXXVII [1]. Heptaiodides(3-) of Ammine Complexes of Chromium and Cobalt: Hexamminechromium(III) heptaiodide [Cr(NH3)6](I3)(I4) and the Tri-μ-hydroxo-bis[metal(III)-triammine] heptaiodides [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Co, Cr
  9. Functionalized 1,1-Ethene Dithiolates as Ligands, V [1]. Synthesis and Crystal Structure of Palladium(II) and Platinum(II) Complexes with Dithioylidene Barbituric Acid Ligands. Molecular Structure of a 2,6-Diaminopyridine-Platinum(II) Barbiturate Complex
  10. Solvothermal Synthesis and Crystal Structure Determination of Tris- (ethyleneamine-ammonium) Tetraselenoantimonat: Non-Centrosymmetry Mediated by an Extended Unusual N-H···N Hydrogen Bonded Network?
  11. Thermische Zersetzung und Lösungskalorimetrie von Ammoniumeuropiumchloriden / Thermal Decomposition and Solution Calorimetry of Ammonium Europium Chlorides
  12. Photochemical Reductive Elimination of Nitrogen from Triazidogallium(III). Generation of Luminescent Gallium(I)
  13. Zur Existenz von [ReNCl4-nFn]- (n = 1-3) Nitridorhenat(VI)-Gemischt- ligandkomplexen -Eine EPR-Untersuchung / EPR Evidence of [ReNCl4-n FnJ– (n = 1-3) Nitridorhenate(VI) Mixed-Ligand Complexes
  14. Synthesis and Crystal Structure of N-[(15,4R)-2-Oxo-pinanyl]-β-alanine Methylester
  15. Synthesis and Conformation of Nucleoside 5'-S-Thiosulfates
  16. Niedere Hydrate aliphatischer primärer Amine. Neue Untersuchungen zu Bildung und Struktur [1] / Lower Hydrates of Aliphatic Primary Amines. New Studies of Formation and Structure [1]
  17. Synthesis and Dimroth Rearrangement of 6-Cyano-l,2,4-triazolo- [4,3-a]pyrimidin-5- and 7-ones. A Novel Alkylation with Orthoesters and a New Participation of the Cyano Group in the Rearrangement
  18. Synthesis and Thermal Properties of Twin Compounds, Alkanediacids 4-(4'-Cyano)-biphenyl Diesters
  19. Synthesis of Pyrrolo-, Thienopyrrolo-, Benzothienopyrroloquinolines as well as Triazoloindole Derivatives
  20. Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests
  21. Preparation and Crystal Structure of Cs4Nb2S11
  22. On the Metalation of 2,6-Dimethyl-4-tert-butyl-thiophenol
  23. Kristallstruktur des Oxo-Acetatkomplexes [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] / Crystal Structure of the Oxo-Acetate Complex [Co7(μ4 -O)2(O2CCH3)10(OPEt3)2]
  24. Penol Catalyzed Claisen ortho Ester Rearrangment of Allylic Alcohols with Trimethyl-β-hoxy) ortho Propionate
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