Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (), [Ir(cod)(NO)(dpp-bian)](BF) () and [Ir(cod)(dpp-bian)](BF) (), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of - feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for ) or a NO group (for ) to complete a square-pyramidal geometry. In the nitrosyl complex , the Ir-N-O group has a bent geometry (the angle is 125°).

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and N NMR Studies of [{Re(μ-X)}(N)] (X = Br or I).

Azide cluster complexes [{Re(μ-Br)}(N)] and [{Re(-I)}(N)] were obtained by reaction of ReX (X = Br or I, respectively) with sodium azide in methanol. The complexes were crystallized as cesium salts of the compositions Cs[{Re(μ-Br)}(N)]·HO () and Cs[{Re(μ-I)}(N)]·HO () and characterized by X-ray single-crystal diffraction and elemental analyses, mass spectrometry, N NMR spectroscopy, and DFT calculations. In the anions, each rhenium atom is coordinated by three azide ligands.

The Theoretical and Experimental Investigation of the Fluorinated Palladium β-Diketonate Derivatives: Structure and Physicochemical Properties.

To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CHCXCHCO(R))] with β-diketone [tfa-1,1,1-trifluoro-2,4-pentanedionato (); pfpa-5,5,6,6,6-pentafluoro-2,4-hexanedionato (); hfba-5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato ()] and β-iminoketone [i-tfa-1,1,1-trifluoro-2-imino-4-pentanonato (); i-pfpa-5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato ()] ligands were synthesized with 70-80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd β-diketonates contained both and isomers, while only isomers were detected in the solutions of Pd β-iminoketonates. The molecules - and new polymorphs of complexes and were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands.

Chirality and Relativistic Effects in Os(CO).

The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os(CO) with D and D symmetries using density functional theory (DFT) methods. The calculations took into account various levels of relativistic effects, including those associated with nonconservation of spatial parity. It was shown that the ground state of Os(CO) corresponds to the D symmetry and thus may be characterized either as left-twisted (D) or right-twisted (D).

Parity violating energy difference for mirror conformers of DABCO linker between two M cations (M = Zn, Cd, and Hg).

We have studied the potential energy surface of cations (M = Zn, Cd, and Hg), which are considered as a model for the DABCO linker in metal-organic frameworks, a new prospective class of materials. Relativistic four-component and two-component calculations of parity violating energy difference (PVED) for twisted isomers of cations have been performed. The right-twisted conformers of are more stable than the left-twisted ones.

A Localized Molecular Orbital Study of the Halogen Substitution Effect on (103)Rh NMR Shielding in [Cp*RhX2]2, Where X = Cl, Br, or I.

(103)Rh NMR parameters and the bonding structure of three complexes of [Cp*RhX2]2, where X = Cl, Br, or I, have been studied with the help of natural bond orbitals (NBOs) and natural localized molecular orbitals (NLMOs). The complexes of [Cp*RhX2]2, where X = Cl, Br, or I, have similar bonding structures, with the major difference being in the degree of covalency of the Rh-X bonds. The decomposition of (103)Rh NMR shielding into diamagnetic, paramagnetic, and spin-orbit terms shows that normal halogen dependence (NHD) of the (103)Rh NMR shift is defined mostly by the paramagnetic term, with the spin-orbit term being significantly smaller.