title: Structural characterization of the manganese(IV) Schiff-base complex MnIV(5-Cl-SALAHP)2.
abstract: Bis[3-(5-chlorosalicylideneamino)propanolato-O,N,O']manganes e(IV) methanol solvate, [Mn(C10H10ClNO2)2].CH3OH, Mr = 510.3, monoclinic, P2(1)/c, a = 11.949 (2), b = 7.530 (2), c = 25.777 (6) A, beta = 105.75 (2) degrees, V = 2232.4 (8) A3, Z = 4, Dx = 1.518 g cm-3, lambda(Mo K alpha) = 0.7107 A, mu = 7.98 cm-1, F(000) = 1502, T = 300 K, R = 0.0343, wR = 0.032 for 2113 unique reflections with (I) greater than 3 sigma(I). The title complex MnIV(5-Cl-SALAHP)2 [5-Cl-SALAHP = 3-(5-chlorosalicylideneamino)propanolato] displays a regular octahedral geometry. The 5-Cl-SALAHP ligand is tridentate, forming a meridional chelate with one phenolato oxygen (Mn-Oavg = 1.90 A), one alkoxide oxygen (Mn-Oavg = 1.85 A) and one imine nitrogen (Mn-Navg = 2.02 A) coordinated to the metal. Important angles described by the six atoms bound to manganese are all very close to either 180 or 90 degrees except the N-Mn-N angle which is 174.7 degrees. Previous studies have shown that MnIV(5-Cl-SALAHP)2 displays a rhombic EPR spectrum with well-resolved 55Mn hyperfine structure on gx, gy and gz. In contrast, Mn(SALADHP)2 [SALADHP = 2-methyl-2-(salicylideneamino)-1,3-propanediolato] shows a broad, ill-defined signal at g = 5.15 and a weak g = 2 component. The different spectral forms result from the extent of distortion of the MnIV octahedron. The reported structure is of potential importance to the understanding of the photosynthetic water-oxidizing system.
authors.affiliation: Department of Chemistry, University of Michigan, Ann Arbor 48109.
authors.forename: X H
authors.initials: XH
authors.lastname: Li
authors.forename: M S
authors.initials: MS
authors.lastname: Lah
authors.forename: V L
authors.initials: VL
authors.lastname: Pecoraro
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds; D012545:Schiff Bases; D013696:Temperature; D014961:X-Ray Diffraction
chemical_list: D009942:Organometallic Compounds; D012545:Schiff Bases; C062582:bis(3-(5-chlorosalicylideneamino)propanolato-O,N-O')manganese(IV)