Structure determination of two metal-organic complexes from high-resolution synchrotron powder diffraction data

Abstract

The crystal structures of [1,2-bis(2,6-diisopropylphenylimino)acenaphthene-N,N']carbonylchlororhodium(I) (1) and [N,N'-ethylene-bis(3-methylsalicylideneiminato)-O,N,N',O'](tetrahydrofurfuryl)-cobalt(II) (2) have been determined from high-resolution synchrotron X-ray powder diffraction data. Compound 1 is the first neutral Rh complex, in contrast with findings in the literature, containing a bidentate nitrogen ligand, and compound 2 is the first three-dimensional structure of a (five-coordinated) tetrahydrofurfurylcobalt(III) complex. Grid-search and Rietveld refinement have been used to determine and refine the structures, respectively. Crystals of 1 are orthorhombic, space group Pbca, Z = 8, with cell parameters a = 21.729 (2), b = 27.376 (3), c = 11.580 (1) A. Crystals of 2 are monoclinic, space group P2(1)/n, Z = 4, a = 16.6701 (6), b = 9.4170 (4), c = 13.7088 (7) A and beta = 96.520 (3) degrees. Chemical diagrams for the two compounds are given. Soft restraints were applied during Rietveld refinement; for 1 converging to R(p) = 8.4%, R(w) = 11.0%, GoF = 2.3, and for 2 converging to R(p) = 8.5%, R(w) = 11.4%, GoF = 7.6.

Strongly Nucleophilic RhI Centre in Square‐Planar Complexes with Terdentate (κ3) 2,2′:6′,2′′‐Terpyridine Ligands: Crystallographic, Electrochemical and Density Functional Theoretical Studies

“…The subsequent thermal reaction of the radical anions most likely involves release of the halide ligand to compensate for the high electron density at the metal centre. Slow halide dissociation also occurs with the radical anion of the much less electron‐rich complex [RhCl(CO)( i Pr 2 Ph‐BIAN)] [ i Pr 2 Ph‐BIAN = N , N′ ‐1,2‐bis(2,6‐diisopropylphenylimino)acenaphthene] 29,30…”