RESUMO
The title compounds, [FeCl2(C15H20N2)4], (I), [FeBr2(C15H20N2)4], (II), and [FeBr2(C15H20N2)4]·2C4H10O, (IIb), respectively, all have triclinic symmetry, with (I) and (II) being isotypic. The Fe(II) atoms in each of the structures are located on an inversion center. They have octa-hedral FeX 2N4 (X = Cl and Br, respectively) coordination spheres with the Fe(II) atom coordinated by two halide ions in a trans arrangement and by the tertiary N atom of four aryl-imidazole ligands [1-(2,6-diiso-propyl-phen-yl)-1H-imidazole] in the equatorial plane. In the two independent ligands, the benzene and imidazole rings are almost normal to one another, with dihedral angles of 88.19â (15) and 79.26â (14)° in (I), 87.0â (3) and 79.2â (3)° in (II), and 84.71â (11) and 80.58â (13)° in (IIb). The imidazole rings of the two independent ligand mol-ecules are inclined to one another by 70.04â (15), 69.3â (3) and 61.55â (12)° in (I), (II) and (IIb), respectively, while the benzene rings are inclined to one another by 82.83â (13), 83.0â (2) and 88.16â (12)°, respectively. The various dihedral angles involving (IIb) differ slightly from those in (I) and (II), probably due to the close proximity of the diethyl ether solvent mol-ecule. There are a number of C-Hâ¯halide hydrogen bonds in each mol-ecule involving the CH groups of the imidazole units. In the structures of compounds (I) and (II), mol-ecules are linked via pairs of C-Hâ¯halogen hydrogen bonds, forming chains along the a axis that enclose R 2 (2)(12) ring motifs. The chains are linked by C-Hâ¯π inter-actions, forming sheets parallel to (001). In the structure of compound (IIb), mol-ecules are linked via pairs of C-Hâ¯halogen hydrogen bonds, forming chains along the b axis, and the diethyl ether solvent mol-ecules are attached to the chains via C-Hâ¯O hydrogen bonds. The chains are linked by C-Hâ¯π inter-actions, forming sheets parallel to (001). In (I) and (II), the methyl groups of an isopropyl group are disordered over two positions [occupancy ratio = 0.727â (13):0.273â (13) and 0.5:0.5, respectively]. In (IIb), one of the ethyl groups of the diethyl ether solvent mol-ecule is disordered over two positions (occupancy ratio = 0.5:0.5).
RESUMO
The new diphosphine ligands Ph(2)PC(6)H(4)C(O)X(CH(2))(2)OC(O)C(6)H(4)PPh(2) (1: X=NH; 2: X=NPh; 3: X=O) and Ph(2)PC(6)H(4)C(O)O(CH(2))(2)O(CH(2))(2)OC(O)C(6)H(4)PPh(2) (5) as well as the monophosphine ligand Ph(2)PC(6)H(4)C(O)X(CH(2))(2)OH (4) have been prepared from 2-diphenylphosphinobenzoic acid and the corresponding amino alcohols or diols. Coordination of the diphosphine ligands to rhodium, iridium, and platinum resulted in the formation of the square-planar complexes [(Pbond;P)Rh(CO)Cl] (6: Pbond;P=1; 7: Pbond;P=2; 8: Pbond;P=3), [(Pbond;P)Rh(CO)Cl](2) (9: Pbond;P=5), [(P-P)Ir(cod)Cl] (10: Pbond;P=1; 11: Pbond;P=2; 12: Pbond;P=3), [(Pbond;P)Ir(CO)Cl] (13: Pbond;P=1; 14: Pbond;P=2; 15: Pbond;P=3), and [(Pbond;P)PtI(2)] (18: Pbond;P=2). In all complexes, the diphosphine ligands are trans coordinated to the metal center, thanks to the large spacer groups, which allow the two phosphorus atoms to occupy opposite positions in the square-planar coordination geometry. The trans coordination is demonstrated unambiguously by the single-crystal X-ray structure analysis of complex 18. In the case of the diphosphine ligand 5, the spacer group is so large that dinuclear complexes with ligand 5 in bridging positions are formed, maintaining the trans coordination of the P atoms on each metal center, as shown by the crystal structure analysis of 9. The monophosphine ligand 4 reacts with [[Ir(cod)Cl](2)] (cod=cyclooctadiene) to give the simple derivative [(4)Ir(cod)Cl] (16) which is converted into the carbonyl complex [(4)Ir(CO)(2)Cl] (17) with carbon monoxide. The crystal structure analysis of 16 also reveals a square-planar coordination geometry in which the phosphine ligand occupies a position cis with respect to the chloro ligand. The diphosphine ligands 1, 2, 3, and 5 have been tested as cocatalysts in combination with the catalyst precursors [[Rh(CO)(2)Cl](2)] and [[Ir(cod)Cl](2)] or [H(2)IrCl(6)] for the carbonylation of methanol at 170 degrees C and 22 bar CO. The best results (TON 800 after 15 min) are obtained for the combination 2/[[Rh(CO)(2)Cl](2)]. After the catalytic reaction, complex 7 is identified in the reaction mixture and can be isolated; it is active for further runs without loss of catalytic activity.