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Structural characterization of the ionic title complex, [MgBr(THF)5][Co(dpbz)2]·2THF [THF is tetra­hydro­furan, C4H8O; dpbz is 1,2-bis­(di­phenyl­phosphan­yl)benzene, C30H24P2], revealed a well-separated cation and anion co-crystallized with two THF solvent mol­ecules that inter­act with the cation via weak C—H...O contacts. The geometry about the cobalt center is pseudo­tetra­hedral, as is expected for a d10 metal center, only deviating from an ideal tetra­hedral geometry because of the restrictive bite angles of the bidentate phosphane ligands. Three THF ligands of the cation and one co-crystallized THF solvent mol­ecule are each disordered over two orientations. In the extended structure, the cations and THF solvent mol­ecules are arranged in (100) sheets that alternate with layers of anions, the latter of which show various π-inter­actions, which may explain the particular packing arrangement. 

Structural characterization of the ionic complexes [FeCl 2 (C 26 H 22 P 2 ) 2 ][FeCl 4 ]·0.59CH 2 Cl 2 or [(dppen) 2 FeCl 2 ][FeCl 4 ]·0.59CH 2 Cl 2 (dppen = cis -1,2-bis(diphenylphosphane)ethylene, P 2 C 26 H 22 ) and [FeCl 2 (C 30 H 24 P 2 ) 2 ][FeCl 4 ]·CH 2 Cl 2 or [(dpbz) 2 FeCl 2 ][FeCl 4 ]·CH 2 Cl 2 (dpbz = 1,2-bis(diphenylphosphane)benzene, P 2 C 30 H 24 ) demonstrates trans coordination of two bidentate phosphane ligands (bisphosphanes) to a single iron(III) center, resulting in six-coordinate cationic complexes that are balanced in charge by tetrachloridoferrate(III) monoanions. The trans bisphosphane coordination is consistent will all previously reported molecular structures of six coordinate iron(III) complex cations with a (PP) 2 X 2 ( X = halido) donor set. The complex with dppen crystallizes in the centrosymmetric space group C 2/ c as a partial-occupancy [0.592 (4)] dichloromethane solvate, while the dpbz-ligated complex crystallizes in the triclinic space group P 1 as a full dichloromethane monosolvate. Furthermore, the crystal studied of [(dpbz) 2 FeCl 2 ][FeCl 4 ]·CH 2 Cl 2 was an inversion twin, whose component mass ratio refined to 0.76 (3):0.24 (3). Beyond a few very weak C—H...Cl and C—H...π interactions, there are no significant supramolecular features in either structure.