A Tetramethylplatinum(IV) Complex with 1,1′‐Bis(diphenylphosphanyl)ferrocene Ligands: Reaction with Trifluoroacetic Acid

Abstract

A new tetramethylplatinum(IV) complex [PtMe 4 (dppf)] [2; dppf = 1,1Ј-bis(diphenylphosphanyl)ferrocene], as the first platinum(IV) complex to contain a chelating dppf ligand, was prepared by the reaction of the known dimeric tetramethylplatinum(IV) complex cis,cis-[Me 4 Pt(µ-SMe 2 ) 2 PtMe 4 ] (1) with the biphosphane ligand dppf (2 equiv.) at room temperature by replacement of the SMe 2 ligands with the P ligating atoms of dppf. The single-crystal X-ray structure of complex 2 revealed that the dppf chelating ligand is arranged close to the "synperiplanar-eclipsed" conformation, with a Cp(centroid)···Fe···Cp(centroid) twist angle of 17.6°and a dppf bite angle, P1-Pt1-P2, of 95.77(3)°. This is in contrast to the usually preferred "synclinal-staggered" conformation, in which the Cp(centroid)···Fe···Cp(centroid) twist angle is close to 36°as found in Pt II complexes with chelating dppf ligands,

Cyclometalated platinum(ii) complexes of 2,2′-bipyridine N-oxide containing a 1,1′-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies

“…This spectrum exhibited a doublet of doublet resonance for PtMe protons at δ = 0.03 ppm which coupled to the platinum center ( 2 JPtH = 65.6 Hz) and to two different phosphorus atoms ( 3 JPH = 8.7 and 6.6 Hz) representing the cis and trans coupling constants to the P atoms. 6,18 The platinum coupling constant value obtained for 2 was significantly lower than the observed value for 1 and confirmed the methyl ligand in complex 2 adopts the trans CPtP arrangement. The α and β protons of the dppf ligand appeared as eight broad singlet signals between δ = 3.47-4.97, confirming all hydrogen atoms of the Cp rings are in different environments, i.e.…”

“…1,2,4 The dppf is a biphosphine ligand and can adopts numerous coordination modes in complexes of a range of transition metals. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] These dppf complexes have been utilized in several area such as catalysis, materials science, electrochemistry, and biology. 1,2,7,9,10,[19][20][21] On the other hand, the chemistry of cyclometalated complexes is of great interest because of their use in a wide range of applications.…”

Syntheses, structures, and electrochemical properties of four complexes based on 4-ferrocenylbutyrate ligand

“…Crystal structure of [Pb 6 (l 2 -OOC(CH 2 ) 3 Fc) 2 (l 3 -OOC(CH 2 ) 3 Fc) 2 (l 2 -g 2 -OOC(CH 2 ) 3 Fc) 2 (g 2 -OOC(CH 2 ) 3 Fc) 2 …”

“…For example, the reactions of flexible neutral ligand methylenebis (3,5-dimethylpyrazole) with Zn(II) ion in the presence of various anions can lead to diverse structures, from discrete 0D structures to infinite 1D chains, 2D bilayer, and 3D metal-organic framework [21]. 1,1-(1,4-Butanediyl)bis-1H-benzimidazole (bbbm) is also a flexible linker and has been used to construct many complexes like { [Ni(bbbm) 2 [22,23].…”

“…Due to the fascinating properties of the ferrocene moiety as well as the diversity of ferrocenyl derivatives, coordination chemists are interested in introducing ferrocene group into ligands in order to generate complexes possessing good electrochemical, magnetic and optical properties [1][2][3][4][5][6]. Furthermore, carboxylate group possesses strong coordinating capability and can display versatile coordination modes such as monodentate mode, symmetric bidentate mode, asymmetric bidentate mode, bridging mode, mix-bridging mode and so on [7][8][9][10][11][12].…”