Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase

We characterized the stationary points along the nucleophilic substitution (SN2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M− + CH3X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > SN2 > OI. The OI channel that results in oxidative insertion complex [CH3–M–X]− is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a SN2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M− to Pd, a d10 metal, because the symmetry of their HOMO orbital is different. The back-side attack SN2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invSN2-TS’s are, in general, submerged. The shape of this M− + CH3X SN2 PES is flatter as compared to that of a main-group base like F− + CH3X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH3−X∙··M]− can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH3 + MX− through halogen abstraction or bends the C-X-M angle to continue the back-side SN2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH3–M–X]−, whereas a noncovalent M–X halogen-bond interaction exists for the [CH3–X∙··M]− complex. This work explores competing channels of the M− + CH3X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions.

Four Novel d10 Metal-Organic Frameworks Incorporating Amino-Functionalized Carboxylate Ligands: Synthesis, Structures, and Fluorescence Properties

By employment of amino-functionalized dicarboxylate ligands to react with d10 metal ions, four novel metal-organic frameworks (MOFs) were obtained with the formula of {[Cd(BCPAB)(μ2-H2O)]}n (1), {[Cd(BDAB)]∙2H2O∙DMF}n (2), {[Zn(BDAB)(BPD)0.5(H2O)]∙2H2O}n (3) and {[Zn(BDAB)(DBPB)0.5(H2O)]∙2H2O}n (4) (H2BCPAB = 2,5-bis(p-carbonylphenyl)-1-aminobenzene; H2BDAB = 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene); BPD = (4,4′-bipyridine); DBPB = (E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; DMF = N,N-dimethylformamide). Complex 1 is a three-dimensional (3D) framework bearing seh-3,5-Pbca nets with point symbol of {4.62}{4.67.82}. Complex 2 exhibits a 4,4-connected new topology that has never been reported before with point symbol of {42.84}. Complex 3 and 4 are quite similar in structure and both have 3D supramolecular frameworks formed by 6-fold and 8-fold interpenetrated 2D coordination layers. The structures of these complexes were characterized by single crystal X-ray diffraction (SC-XRD), thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements. In addition, the fluorescence properties and the sensing capability of 2–4 were investigated as well and the results indicated that complex 2 could function as sensor for Cu2+ and complex 3 could detect Cu2+ and Ag+via quenching effect.

Hg3(Te3O8)(SO4): A New Sulfate Tellurite with Novel Structure and Large Birefringence Explored from d10 Metal Compounds

Our explorations of novel inorganic solids with large birefringence in d10 Metal-Te4+-SO42- system afforded four new sulfate tellurites, Ga2(TeO3)(SO4)(OH)2, In2(TeO3)2(SO4)(H2O), Zn4(Te3O7)2(SO4)2(H2O) and Hg3(Te3O8)(SO4). Notably, Hg3(Te3O8)(SO4) exhibits the largest birefringence at...

Hydrogen bond synthons affect coordination geometry of d10-metal halide complexes: Synthetic methods, theoretical studies and supramolecular architectures

In this study, five new d10-metal halide coordination compounds, namely [HgCl2(L)]n (1), [HgBr2(L)]n (2), [HgI2(L)]n (3), [ZnCl2(L)2] (4) and [CdI2(L)2]n (5) (L is N-(3-pyridinyl)-2-pyrazine carboxamide ligand) have been prepared by...

Two luminescent d10 metal coordination polymers based on 3-nitro-5-(pyridin-3-yl)benzoic acid

Two new coordination polymers (CPs), [Zn(npba)2] (1) and [Cd(npba)2] (2), have been hydrothermally synthesized from Zn(NO3)2·6H2O/Cd(NO3)2·6H2O and 3-nitro-5-(pyridin-3-yl) benzoic acid (Hnpba). The products have been characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. In CP 1, the four-coordinated Zn(II) centers are bridged by npba ligands to generate chains, which are connected through arene π–π stacking interactions to generate a layer structure. In CP 2, the six-coordinated Cd(II) centers are also bridged by npba ligands to form chains with similar connectivity. The photoluminescence properties of CPs 1 and 2 were studied.