The complex Ru(TPP)(NAr)(2) inserts a nitrene group into allylic and benzylic C-H bonds and is the key intermediate in the ruthenium porphyrin-catalyzed amination of hydrocarbons by aryl azides.
This paper describes the synthesis of allylic amines by aryl azides (ArN 3 ) catalysed by [Ru(TPP)CO] (TPP = dianion of tetraphenylporphyrin). The employment of aryl azides renders the methodology sustainable as the formation of molecular nitrogen is the only stoichiometric byproduct. The isolation of catalytic intermediates and spectroscopic and kinetic studies revealed interesting information about the reaction mechanism, which could improve its catalytic efficiency in future research. An important result is the X-ray characteri-
The effect of pressure on the dinuclear spin crossover material [{Fe(bpp)(NCS)(2)}(2)(4,4'-bipy)]·2MeOH (where bpp = 2,6-bis(pyrazol-3-yl)pyridine and 4,4'-bipy = 4,4'-bipyridine, 1) has been investigated with single crystal X-ray diffraction and Raman spectroscopy using diamond anvil cell techniques. The very gradual pressure-induced spin crossover occurs between 7 and 25 kbar, and shows no evidence of crystallographic phase transitions. The pressure-induced spin transition leads to a complete LS state which is not thermally accessible. This structural evolution under pressure is in stark contrast to the previously reported thermal spin crossover behaviour, in which a symmetry-breaking, purely structural phase transition results in only partial conversion to the low spin state. This observation is attributed to the symmetry-breaking phase transition becoming unfavourable under pressure.
Mixed M(II)/M(III) metal oxalates, as "stripes" connected through strong hydrogen bonding by para-dimethylaminobenzaldeide (DAMBA) and water, form an organic-inorganic 2D network that enables segregation in layers of the cationic organic NLO-phore trans-4-(4-dimethylaminostyryl)-1-methylpyridinium, [DAMS+]. The crystalline hybrid materials obtained have the general formula [DAMS]4[M2M'(C2O4)6].2DAMBA.2H2O (M = Rh, Fe, Cr; M' = Mn, Zn), and their overall three-dimensional packing is non-centrosymmetric and polar, therefore suitable for second harmonic generation (SHG). All the compounds investigated are characterized by an exceptional SHG activity, due both to the large molecular quadratic hyperpolarizability of [DAMS+] and to the efficiency of the crystalline network which organizes [DAMS+] into head-to-tail arranged J-type aggregates. The tunability of the pairs of metal ions allows exploiting also the magnetic functionality of the materials. Examples containing antiferro-, ferro-, and ferri-magnetic interactions (mediated by oxalato bridges) are obtained by coupling proper M(III) ions (Fe, Cr, Rh) with M(II) (Mn, Zn). This shed light on the role of weak next-nearest-neighbor interactions and main nearest-neighbor couplings along "stripes" of mixed M(II)/M(III) metal oxalates of the organic-inorganic 2D network, thus suggesting that these hybrid materials may display isotropic 1D magnetic properties along the mixed M(II)/M(III) metal oxalates "stripes".
Single crystal X-ray diffraction of oxalic acid dihydrate H(2)C(2)O(4).2H(2)O (1), at pressures up to 5.3 GPa, shows significant changes in the molecular geometries, probably accompanied by a proton migration from H(2)C(2)O(4) to H(2)O and formation of ionic species, as predicted by periodic DFT calculations.
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