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Papers by tp tp
Inorganic Chemistry, 2000
The bis(ethylene) Rh species Tp Me2 Rh(C 2 H 4 ) 2 (1*) (Tp Me2 ) tris(3,5-dimethyl-1-pyrazol-1-y... more The bis(ethylene) Rh species Tp Me2 Rh(C 2 H 4 ) 2 (1*) (Tp Me2 ) tris(3,5-dimethyl-1-pyrazol-1-yl)hydroborate) has been obtained from [RhCl(C 2 H 4 ) 2 ] 2 and KTp Me2 . Complex 1* easily decomposes in solution to give mainly the butadiene species Tp Me2 Rh(η 4 -C 4 H 6 ). In the solid state its thermal decomposition follows a different course and the allyl Tp Me2 RhH(syn-C 3 H 4 Me) is cleanly obtained as a mixture of exo and endo isomers. The complexes Tp′Rh-(C 2 H 4 ) 2 (Tp′ ) Tp, Tp Me2 ) afford the monosubstituted species Tp′Rh(C 2 H 4 )(PR 3 ) upon reaction with PR 3 but react differently with L ) CO or CNR: the Tp compound gives dinuclear [TpRh] 2 (µ-L) 3 complexes, while, in the case of 1*, Tp Me2 Rh(C 2 H 4 )(L) species are obtained. The ethylene ligand of complexes Tp Me2 Rh(C 2 H 4 )(PR 3 ) is labile, and several peroxo compounds of composition Tp Me2 Rh(O 2 )(PR 3 ) have been isolated by their reaction with O 2 . All the mononuclear Rh(I) complexes are formulated as 18etrigonal bipyramidal species on the basis of IR and NMR spectroscopic studies. A series of dihydride complexes of Rh(III) of formulation Tp′RhH 2 (PR 3 ) have been prepared by the hydrogenation of the corresponding ethylene derivatives. Complexes [TpRh] 2 (µ-CNCy) 3 , Tp Me2 Rh(C 2 H 4 )(PEt 3 ), and Tp Me2 Rh(O 2 )(PEt 3 ) have been further characterized by X-ray diffraction studies.
![Research paper thumbnail of Complexes of main-group elements containing stereochemically active lone pairs: the crystal structures of [Tl(Tp An)] {Tp An=tris[3-(2-methoxyphenyl)pyrazol-1-yl]hydroborate} and [Pb(Tp Py)(NO 3)]·0.5Et 2O {Tp Py = tris[3,-(2-pyrdyl)pyrazol-1-yl]hydroborate](https://attachments.academia-assets.com/48160474/thumbnails/1.jpg)
](Polyhedron, 1997
The new podand ligand tris[3-(2-methoxyphenyl)pyrazol-l-yl]hydroborate (Tp A°) has been prepared ... more The new podand ligand tris[3-(2-methoxyphenyl)pyrazol-l-yl]hydroborate (Tp A°) has been prepared and the crystal structure of [TI(TpAn)] determined. The metal ion is in a trigonal pyramidal geometry arising from the three pyrazolyl N-donors, with the lone pair of the T11 ion in the fourth position of the tetrahedron of electron pairs. There is also a weak but significant interaction with one of the anisyl oxygen atoms (T1...O = 3.018 ~), and the displacement of the metal ion towards this oxygen atom results in a noticeable lengthening of the TI--N(pyrazolyl) bond which lies approximately trans to it (2.70 &, compared with 2.54/~ for the other two T1--N bonds). The crystal structure of [Pb(TpPY)(NO3)] "0.5Et20 shows that the Pb n ion has four strong interactions (with the pyrazolyl nitrogen atoms and one of the nitrate oxygen atoms; range of bond lengths 2.49-2.67 A) and four weak ones (with the pyridyl nitrogen atoms and the other nitrate oxygen atom; range of bond lengths 2.80-2.99 ,~). If only the four stronger interactions are considered, the irregular coordination sphere of the Pb H ion has an obvious gap in it which is the site of the stereochemically active lone pair.
Journal of Molecular Catalysis A-chemical, 2004
... However, an alternative method that has recently received attention consists in the use of a ... more ... However, an alternative method that has recently received attention consists in the use of a binary system where one catalyst produces 1-alkenes in situ and the another one polymerizes ethylene and incorporates the 1-alkene into the growing chain [3]. This process has the ...
Inorganic Chemistry, 1997
The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hyd... more The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hydrotris(3-phenylpyrazolyl)borate (KTp(Ph)) leads to the formation of the blood-red bis(ligand) complex [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))]. This compound crystallizes in the monoclinic space group P2(1)/n, with a = 10.690(5) Å, b = 34.243(15) Å, c = 12.923(4) Å, beta = 96.17(3) degrees, Z = 4, V = 4703(3) Å(3), and R = 0.040. The molecular structure contains a square CoN(5) pyramid with an agostic BH.Co interaction of 2.17(2) Å. One Tp(Ph) ligand acts tridentate; the other, bidentate. The reaction of KTp(Ph) with zinc and cobalt halides yields a series of heteroleptic halogeno complexes [(Tp(Ph))MX]. The zinc species are all tetrahedral, while in the case of cobalt(II) the UV-vis spectra indicate an equilibrium of tetra- and pentacoordinated species depending on the anion size and the donor properties of the solvent. Metathesis reactions with carboxylates yield mononuclear complexes [(Tp(Ph))M(O(2)CR)]; M = Zn(II), Co(II); RCO(2)(-) = acetate, benzoate, 4-fluorobenzoate, and 4-nitrobenzoate. The infrared bands nu(as)(CO(2)) and nu(sym)(CO(2)) indicate monodentate carboxylate ligands in the zinc complexes in the solid state and in solution. The cobalt complexes [(Tp(Ph))Co(carboxylate)] are dark blue in dichloromethane and in the solid state when grown from dichloromethane solution. Tetrahydrofuran solutions and crystals grown from tetrahydrofuran are pink, purple, or reddish violet. The 2-aminobenzoate (anthranilate) complexes [(Th(Ph))M(anthranilate)], M = Zn(II), Co(II), have been prepared. [(eta(3)-Tp(Ph))Zn(anthranilate)] crystallizes in the monoclinic space group P2(1)/n, with a = 13.205(4) Å, b = 15.643(3) Å, c = 15.116(3) Å, beta = 98.86(2) degrees, Z = 4, V = 3085(1) Å(3), and R = 0.034. Anthranilate acts as a chelating oxygen ligand with Zn-O distances of 1.932(2) and 2.460(2) Å. The amino group is not involved in metal coordination. The reaction of the chloro complexes [(Tp(Ph))MCl] with sodium or potassium acetylacetonate leads to isotypic zinc and cobalt complexes [(eta(3)-Tp(Ph))M(eta(2)-acac)]. Both crystallize in the monoclinic space group P2(1)/c, with Z = 4, the zinc compound with a = 16.334(3) Å, b = 11.545(2) Å, c = 15.816(3) Å, beta = 94.77(1) degrees, V = 2972(1) Å(3), and R = 0.039 and the cobalt compound with a = 16.358(7) Å, b = 11.519(2) Å, c = 15.847(6) Å, beta = 95.30(3) degrees, V = 2973(2) Å(3), and R = 0.035. The structures are best described as slightly distorted trigonal bipyramids with the two axial positions occupied by one of the acetylacetonate O and one of the tripodal N donor atoms. Ligand profiles of Tp(Ph) and related ligands have been calculated to visualize the angular encumbrance of the ligands.
Inorganica Chimica Acta, 2003
A novel one-dimensional vanadium(V)-organic coordination polymer [{VO 2 (2,2′-bipy)} 2 (tp)] ∞ (1... more A novel one-dimensional vanadium(V)-organic coordination polymer [{VO 2 (2,2′-bipy)} 2 (tp)] ∞ (1) has been hydrothermally synthesized from the reaction of V 2 O 5 , 2,2′-bipyridine, and terephthalate. It has been characterized by IR, XPS, TGA and single-...
Cancer Immunology Immunotherapy, 1990
Swiss male mice were immunosuppressed by cyclophosphamide, cisplatinum, vincristine and methotrex... more Swiss male mice were immunosuppressed by cyclophosphamide, cisplatinum, vincristine and methotrexate. The ability of the thymopoietin (TP) fragments TP-3, TP-4 and TP-5 to restore antibody production and phagocytosis was studied. Impaired antibody production after vincristine treatment was partially or totally restored by TP-3, TP-4 or TP-5. Only TP-3 or TP-5 interfered with the antibody-production-damaging effect of cisplatinum. The same effect of methotrexate could not be influenced by any of the TP fragments. The phagocytic capacity of peritoneal macrophages was reduced by vincristine, methotrexate and cyclophosphamide treatment. In this respect, TP-3 protected the function of macrophages against vincristine and cyclophosphamide treatment. TP-4 was active in the case of damage caused by vincristine and methotrexate, and TP-5 interfered with the phagocytosis-inhibiting effect of methotrexate. Each TP fragment seems to have a specific target orientation within the immune system. This also means that the proper TP fragment should always be chosen for combination therapy with various types of cytotoxic drugs.
Inorganic Chemistry, 2000
The bis(ethylene) Rh species Tp Me2 Rh(C 2 H 4 ) 2 (1*) (Tp Me2 ) tris(3,5-dimethyl-1-pyrazol-1-y... more The bis(ethylene) Rh species Tp Me2 Rh(C 2 H 4 ) 2 (1*) (Tp Me2 ) tris(3,5-dimethyl-1-pyrazol-1-yl)hydroborate) has been obtained from [RhCl(C 2 H 4 ) 2 ] 2 and KTp Me2 . Complex 1* easily decomposes in solution to give mainly the butadiene species Tp Me2 Rh(η 4 -C 4 H 6 ). In the solid state its thermal decomposition follows a different course and the allyl Tp Me2 RhH(syn-C 3 H 4 Me) is cleanly obtained as a mixture of exo and endo isomers. The complexes Tp′Rh-(C 2 H 4 ) 2 (Tp′ ) Tp, Tp Me2 ) afford the monosubstituted species Tp′Rh(C 2 H 4 )(PR 3 ) upon reaction with PR 3 but react differently with L ) CO or CNR: the Tp compound gives dinuclear [TpRh] 2 (µ-L) 3 complexes, while, in the case of 1*, Tp Me2 Rh(C 2 H 4 )(L) species are obtained. The ethylene ligand of complexes Tp Me2 Rh(C 2 H 4 )(PR 3 ) is labile, and several peroxo compounds of composition Tp Me2 Rh(O 2 )(PR 3 ) have been isolated by their reaction with O 2 . All the mononuclear Rh(I) complexes are formulated as 18etrigonal bipyramidal species on the basis of IR and NMR spectroscopic studies. A series of dihydride complexes of Rh(III) of formulation Tp′RhH 2 (PR 3 ) have been prepared by the hydrogenation of the corresponding ethylene derivatives. Complexes [TpRh] 2 (µ-CNCy) 3 , Tp Me2 Rh(C 2 H 4 )(PEt 3 ), and Tp Me2 Rh(O 2 )(PEt 3 ) have been further characterized by X-ray diffraction studies.
Polyhedron, 1997
The new podand ligand tris[3-(2-methoxyphenyl)pyrazol-l-yl]hydroborate (Tp A°) has been prepared ... more The new podand ligand tris[3-(2-methoxyphenyl)pyrazol-l-yl]hydroborate (Tp A°) has been prepared and the crystal structure of [TI(TpAn)] determined. The metal ion is in a trigonal pyramidal geometry arising from the three pyrazolyl N-donors, with the lone pair of the T11 ion in the fourth position of the tetrahedron of electron pairs. There is also a weak but significant interaction with one of the anisyl oxygen atoms (T1...O = 3.018 ~), and the displacement of the metal ion towards this oxygen atom results in a noticeable lengthening of the TI--N(pyrazolyl) bond which lies approximately trans to it (2.70 &, compared with 2.54/~ for the other two T1--N bonds). The crystal structure of [Pb(TpPY)(NO3)] "0.5Et20 shows that the Pb n ion has four strong interactions (with the pyrazolyl nitrogen atoms and one of the nitrate oxygen atoms; range of bond lengths 2.49-2.67 A) and four weak ones (with the pyridyl nitrogen atoms and the other nitrate oxygen atom; range of bond lengths 2.80-2.99 ,~). If only the four stronger interactions are considered, the irregular coordination sphere of the Pb H ion has an obvious gap in it which is the site of the stereochemically active lone pair.
Journal of Molecular Catalysis A-chemical, 2004
... However, an alternative method that has recently received attention consists in the use of a ... more ... However, an alternative method that has recently received attention consists in the use of a binary system where one catalyst produces 1-alkenes in situ and the another one polymerizes ethylene and incorporates the 1-alkene into the growing chain [3]. This process has the ...
Inorganic Chemistry, 1997
The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hyd... more The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hydrotris(3-phenylpyrazolyl)borate (KTp(Ph)) leads to the formation of the blood-red bis(ligand) complex [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))]. This compound crystallizes in the monoclinic space group P2(1)/n, with a = 10.690(5) Å, b = 34.243(15) Å, c = 12.923(4) Å, beta = 96.17(3) degrees, Z = 4, V = 4703(3) Å(3), and R = 0.040. The molecular structure contains a square CoN(5) pyramid with an agostic BH.Co interaction of 2.17(2) Å. One Tp(Ph) ligand acts tridentate; the other, bidentate. The reaction of KTp(Ph) with zinc and cobalt halides yields a series of heteroleptic halogeno complexes [(Tp(Ph))MX]. The zinc species are all tetrahedral, while in the case of cobalt(II) the UV-vis spectra indicate an equilibrium of tetra- and pentacoordinated species depending on the anion size and the donor properties of the solvent. Metathesis reactions with carboxylates yield mononuclear complexes [(Tp(Ph))M(O(2)CR)]; M = Zn(II), Co(II); RCO(2)(-) = acetate, benzoate, 4-fluorobenzoate, and 4-nitrobenzoate. The infrared bands nu(as)(CO(2)) and nu(sym)(CO(2)) indicate monodentate carboxylate ligands in the zinc complexes in the solid state and in solution. The cobalt complexes [(Tp(Ph))Co(carboxylate)] are dark blue in dichloromethane and in the solid state when grown from dichloromethane solution. Tetrahydrofuran solutions and crystals grown from tetrahydrofuran are pink, purple, or reddish violet. The 2-aminobenzoate (anthranilate) complexes [(Th(Ph))M(anthranilate)], M = Zn(II), Co(II), have been prepared. [(eta(3)-Tp(Ph))Zn(anthranilate)] crystallizes in the monoclinic space group P2(1)/n, with a = 13.205(4) Å, b = 15.643(3) Å, c = 15.116(3) Å, beta = 98.86(2) degrees, Z = 4, V = 3085(1) Å(3), and R = 0.034. Anthranilate acts as a chelating oxygen ligand with Zn-O distances of 1.932(2) and 2.460(2) Å. The amino group is not involved in metal coordination. The reaction of the chloro complexes [(Tp(Ph))MCl] with sodium or potassium acetylacetonate leads to isotypic zinc and cobalt complexes [(eta(3)-Tp(Ph))M(eta(2)-acac)]. Both crystallize in the monoclinic space group P2(1)/c, with Z = 4, the zinc compound with a = 16.334(3) Å, b = 11.545(2) Å, c = 15.816(3) Å, beta = 94.77(1) degrees, V = 2972(1) Å(3), and R = 0.039 and the cobalt compound with a = 16.358(7) Å, b = 11.519(2) Å, c = 15.847(6) Å, beta = 95.30(3) degrees, V = 2973(2) Å(3), and R = 0.035. The structures are best described as slightly distorted trigonal bipyramids with the two axial positions occupied by one of the acetylacetonate O and one of the tripodal N donor atoms. Ligand profiles of Tp(Ph) and related ligands have been calculated to visualize the angular encumbrance of the ligands.
Inorganica Chimica Acta, 2003
A novel one-dimensional vanadium(V)-organic coordination polymer [{VO 2 (2,2′-bipy)} 2 (tp)] ∞ (1... more A novel one-dimensional vanadium(V)-organic coordination polymer [{VO 2 (2,2′-bipy)} 2 (tp)] ∞ (1) has been hydrothermally synthesized from the reaction of V 2 O 5 , 2,2′-bipyridine, and terephthalate. It has been characterized by IR, XPS, TGA and single-...
Cancer Immunology Immunotherapy, 1990
Swiss male mice were immunosuppressed by cyclophosphamide, cisplatinum, vincristine and methotrex... more Swiss male mice were immunosuppressed by cyclophosphamide, cisplatinum, vincristine and methotrexate. The ability of the thymopoietin (TP) fragments TP-3, TP-4 and TP-5 to restore antibody production and phagocytosis was studied. Impaired antibody production after vincristine treatment was partially or totally restored by TP-3, TP-4 or TP-5. Only TP-3 or TP-5 interfered with the antibody-production-damaging effect of cisplatinum. The same effect of methotrexate could not be influenced by any of the TP fragments. The phagocytic capacity of peritoneal macrophages was reduced by vincristine, methotrexate and cyclophosphamide treatment. In this respect, TP-3 protected the function of macrophages against vincristine and cyclophosphamide treatment. TP-4 was active in the case of damage caused by vincristine and methotrexate, and TP-5 interfered with the phagocytosis-inhibiting effect of methotrexate. Each TP fragment seems to have a specific target orientation within the immune system. This also means that the proper TP fragment should always be chosen for combination therapy with various types of cytotoxic drugs.