Trinuclear Mn2+/Zn2+ based microporous coordination polymers as efficient catalysts for ipso-hydroxylation of boronic acids.

Two microporous coordination polymers based on hourglass trinuclear building units, [Mn3(bpdc)3(bpy)]·2DMF and [Zn3(bpdc)3(bpy)]·2DMF·4H2O (bpdc = 4,4'-biphenyl dicarboxylic acid, bpy = 4,4'-bipyridine), have been synthesized under solvothermal conditions employing DMF as the solvent. Each structure consists of two crystallographically distinct M2+ (M1 and M2) centers that are connected via carboxylate bridges from six bpdc ligands, generating a trinuclear metal cluster, [M3(bpdc)3(bpy)]. Cluster representation of the structure resulted in an interpenetrated net of rare hex topological type. Catalytic activities of the CPs have been assessed for the oxidative hydroxylation of phenylboronic acids (PBAs) using aqueous hydrogen peroxide (H2O2). Various substituted aryl/hetero-arylboronic acids RB(OH)2 [R = phenyl, 2,4-difluorophenyl, 4-aminophenyl, 2-thiophene etc.] underwent ipso-hydroxylation smoothly at room temperature to generate the corresponding phenols in excellent yields. The main advantages of this protocol are the aqueous medium reaction, heterogeneous catalytic system, and short reaction time with excellent yield.

Crystal structure of bis-(µ-4-nitro-benzoato-κ2O:O')bis-[bis-(4-methyl-pyridine-κN)(4-nitro-benzoato-κ2O,O')manganese(II)].

The title compound, [Mn2(C7H4NO4)4(C6H7N)4] or [Mn2(µ-NBz)2(κ2-NBz)2(4-Mepy)4], where NBz is 4-nitro-benzoate and 4-Mepy is 4-methyl-pyridine, is a centrosymmetric dinuclear complex in which the MnII atoms are bridged by two NBz ligands with Mn⋯Mn = 4.1324 (4) Å. The MnII atom in this dimeric species is present in a distorted octa-hedral environment with the four coordinating O atoms forming the equatorial plane and the two pyridyl N atoms occupying the axial sites. An important structural feature of the dimeric complex is that each of the bridging carboxyl-ate ligands binds to the metal ions in an asymmetric fashion involving bent and linear Mn-O-C units. The crystal packing is consolidated by C-H⋯O and C-H⋯π interactions.

Inverse bilayer structure of mononuclear Co(II) and Ni(II) complexes of the type M(H2O)3(SO4)(4-CNpy)2.

Two new metal compounds of the formula [M(H(2)O)(3)(SO(4))(4-CNpy)(2)] x H(2)O [M = Ni (1) and Co (2), 4-CNpy = 4-cyanopyridine] have been prepared and studied by X-ray diffraction. In both of these compounds the 4-CNpy ligands are coordinated via pyridyl-N atoms to the metal ions in a cis fashion. The neutral complexes along with the uncoordinated H(2)O molecules are glued together preferentially into inverse bilayers by non-covalent interactions, including unique interlayer pi-pi interactions between antiparallel nitrile groups. Hartree-Fock and density-functional theory (DFT) calculations indicate that the pi-pi interactions are energetically significant. The unit-cell similarity index (Pi) of 0.0046 for the compounds suggests their isostructurality, which is also supported by their X-ray powder diffraction patterns that can be almost superimposed.

Synthesis, structure, spectral and electrochemical properties, and catalytic use of cobalt(III)-oxo cubane clusters.

Olive-green cobalt(III) complexes having the general formula Co4O4(O2CMe)4L4 (1) where L = py (1a), 4-Mepy (1b), 4-Etpy (1c), and 4-CNpy (1d) have been prepared by the H2O2 oxidation of a mixture of Co2+, MeCO2-, and pyridine or 4-substituted pyridines in a 1:2:1 molar ratio in methanol. Spectroscopic and X-ray crystallographic studies show that these complexes contain a tetrameric cubane-like core [Co4(mu3-O)4]4+ where the four cobalt atoms form an approximate tetrahedron with edge lengths of approximately 2.75 A. Each cobalt in the crystallographically determined structure of Co4(mu3-O)4(mu-O2CMe)4L4 in 1a.NaClO4.3.5H2O and 1b.3H2O is hexacoordinate. Infrared spectra of the complexes show characteristic bands near 700, 635, and 580 cm-1 due to the central cubane-like core. 1H NMR spectra of the complexes show that the dissolved species are essentially diamagnetic and also that the complexes maintain their integrity in solution. UV-vis spectra of the green solutions have been interpreted in terms of ligand-field and charge-transfer bands. The electrochemical behavior of the complexes studied by cyclic and differential pulse voltammetric techniques indicates that the [(CoIII)4(mu3-O)4]4+ core present in the complexes undergoes a reversible one-electron oxidation to the [(CoIII)3CoIV(mu3-O)4]5+ core with an E1/2 value below 1 V. This suggests that these complexes of cobalt may be suitable as catalysts for the oxidation of organic compounds. Preliminary investigations indicate that 1a has a role to play in the cobalt-catalyzed aerobic oxidation of neat ethylbenzene and p-xylene.