0000000000653094
AUTHOR
Bertrand Rebière
Enlarging the family of ferrocenylphosphine dinuclear rhodium complexes: synthesis and X-ray structure of a novel “A-frame”-type trimetallic Rh/Fe/Rh complex
Abstract The symmetrically substituted ligand 1,1 ′ -bis[di(5-methyl-2-furyl)phosphino]ferrocene ( 1 ) has been obtained from the bromophosphine BrP(Fu Me ) 2 and the dilithioferrocene/TMEDA adduct. The quantitative addition of this ferrocene derivative to the tetracarbonyl dimer [(CO) 4 Rh 2 {μ-(S t Bu) 2 }] leads, through decarbonylation, to the dinuclear rhodium complex [(CO) 2 Rh 2 {μ-(S t Bu) 2 }{μ- P , P -Fc[P(Fu Me ) 2 ] 2 }] ( 2 ) in high yield. A X-ray structure [ orthorhombic , space group P 2 1 2 1 2 1 ; a =11.2982(2) A, b =13.3165(3) A, c =27.2687(7) A] and the solution multinuclear NMR characterization are reported, which show that the rare “quasi-closed bridging” A-frame struc…
"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes.
Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constan…
A Bis(diazadiene) Adduct of MoCl 2 : Mononuclear, Octahedral, Undistorted and Diamagnetic
The complex [MoCl2(iPr2dad)2] (iPr2dad = iPrN=CH−CH=N−iPr) is obtained in one step by reduction of [MoCl3(THF)3] in the presence of iPr2dad. The X-ray structure reveals a relatively undistorted octahedral coordination geometry with a relative cis configuration and points to a more appropriate description of the ligands as enediamides. The NMR investigation is in agreement with the same cis structure in solution and underlines the diamagnetism of the compound, at odds with previously reported very similar complexes. A bulk magnetic susceptibility measurement further confirms the compound’s diamagnetism. No equilibrium with a dinuclear, metal-metal bonded species is apparent from the solution…