Coordination chemistry of tetra- and tridentate ferrocenyl polyphosphines: an unprecedented [1,1'-heteroannular and 2,3-homoannular]-phosphorus-bonding framework in a metallocene dinuclear coordination complex
| العنوان: | Coordination chemistry of tetra- and tridentate ferrocenyl polyphosphines: an unprecedented [1,1'-heteroannular and 2,3-homoannular]-phosphorus-bonding framework in a metallocene dinuclear coordination complex |
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| المؤلفون: | Peter N. Horton, Ian R. Butler, Philippe Meunier, Jean-Cyrille Hierso, D. A. Thomas, V. V. Ivanov |
| المساهمون: | Department of Chemistry, University of Wales, University of Wales, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Department of Chemistry, University of Southampton, University of Southampton, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), University of Southampton [Southampton] |
| المصدر: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2008, 47 (5), pp.1607-1615. ⟨10.1021/ic7022105⟩ Inorganic Chemistry, American Chemical Society, 2008, 47 (5), pp.1607-1615. 〈10.1021/ic7022105〉 |
| بيانات النشر: | HAL CCSD, 2008. |
| سنة النشر: | 2008 |
| مصطلحات موضوعية: | crystal structure, Stereochemistry, chemistry.chemical_element, Crystal structure, 010402 general chemistry, 01 natural sciences, Coordination complex, Inorganic Chemistry, chemistry.chemical_compound, nickel, through-space interaction, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Lone pair, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, nuclear spin-spin coupling, 010405 organic chemistry, Ligand, ligands, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, ferrocene, palladium, 0104 chemical sciences, Crystallography, Nickel, chemistry, Ferrocene, polyphosphine, Metallocene, Palladium |
| الوصف: | Palladium(ll) and nickel(ll) halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd 2 Cl 4 (1)] (3b) and nickel [NiCl 2 (5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" 31 P 31 P nuclear spin-spin coupling constants (Jpp) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase. In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 A, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 A in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1. |
| اللغة: | English |
| تدمد: | 0020-1669 1520-510X |
| DOI: | 10.1021/ic7022105⟩ |
| DOI: | 10.1021/ic7022105〉 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::be4ea12dcf0c45315e6ffa16e73ab1d1 https://hal.archives-ouvertes.fr/hal-00460859 |
| رقم الانضمام: | edsair.doi.dedup.....be4ea12dcf0c45315e6ffa16e73ab1d1 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 00201669 1520510X |
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| DOI: | 10.1021/ic7022105⟩ |