878190-65-9Relevant academic research and scientific papers
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
Thomas,Ivanov,Butler,Horton,Meunier,Hierso
, p. 1607 - 1615 (2009/01/30)
Palladium(II) and nickel(II) 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 2Cl4(1)] (3b) and nickel [NiCl2(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 31P31P nuclear spin-spin coupling constants (JPP) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase. In these cases, an intemuclear 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 (intemuclear 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.
General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: Selective synthesis and characterization of a new class of tri- and tetrasubstituted ferrocenyl compounds
Ivanov,Hierso,Amardeil,Meunier
, p. 989 - 995 (2008/10/09)
Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferrocenylphosphines (A-Fe-B). The proposed synthetic method represents a unique means to produce achiral dissymmetric 1,1′,2-substituted ferrocenes (A-Fe-B) bearing a heteroannular 1′-substituent which is different from the homoannular 1- and 2-substituents. The selectivity for the two-step reaction favors formation of the desired dissymmetric product (A-Fe-B) rather than the concurrent formation of the symmetric di- and tetrasubstituted ferrocenes (A-Fe-A and B-Fe-B). Therefore, this method allows access to a great number of dissymmetric multidentate metalloligands, especially when one considers that functionalized-Cp salts continue to expand in terms of number and diversity. Herein, emphasis was placed upon the 1H, 13C, and 31P NMR characterization of the metalloligands; several examples exhibit intriguing conformational properties and rare through-space phosphorus nuclear-spin couplings.
