This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6-e][1,2,3,4]tetrazine 1,3,6,8-tetraoxide (TTTO). It was synthesized in ten steps from 2,2-bis(tert-butyl-NNO-azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4-tetrazine 1,3-dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert-butyl-NNO-azoxy groups. The TTTO structure was confirmed by single-crystal X-ray.

Stereochemically inert and positively charged chiral complexes of cobalt(III) prepared from Schiff bases derived from chiral diamines and salicylaldehydes were shown to be efficient catalysts of the benchmark asymmetric phase‐transfer Michael addition of nine activated olefins to O’Donnell’s substrate. The reaction products had enantiomeric purities of up to 96%. DFT calculations were invoked to rationalize the stereochemistry of the addition.magnified image

The thermodynamics of chloride dissociation from the 18e arene ruthenium iminophosphonamides [(η -arene)RuCl{(R'N) PR }] (1 a-d) [previously known with arene=C Me , R=Ph, R'=p-Tol (a); R=Et, R'=p-Tol (b); R=Ph, R'=Me (c); and new with arene=p-cymene, R=Ph, R'=p-Tol (d)] was assessed in both polar and apolar solvents by variable-temperature UV/Vis, NMR, and 2D EXSY H NMR methods, which highlighted the influence of the NPN ligand on the equilibrium parameters. The dissociation enthalpy ΔH decreases with increasing electron-donating ability of the N- and P-substituents (1 a, 1 d>1 b>1 c) and solvent polarity, and this results in exothermic spontaneous dissociation of 1 c in polar solvents. The coordination of neutral ligands (MeCN, pyridine, CO) to the corresponding 16e complexes [(η -arene)Ru{(R'N) PR }] PF (2 a-d) is reversible; the stability of the 2⋅L adducts depends on the π-accepting ability of L. Carbonylation of 2 a and 2 d resulted in rare examples of cationic arene ruthenium carbonyl complexes (3 a, 3 d), while the monocarbonyl adduct derived from 2 c reacts further with a second equivalent of CO with conversion to carbonyl-carbamoyl complex 3 c, in which one CO molecule is inserted into the Ru-N bond. The new complexes 1 d, 2 d, 3 a, 3 c, and 3 d were isolated and structurally characterized.

Novel half-sandwich 18ē and 16ē arene ruthenium iminophosphonamide complexes [(η-CMe)RuCl{(R'N)PR}] (3a-c) and [(η-CMe)Ru{(R'N)PR}](X) (4a-c) (a, R = Ph, R' = p-Tol; b, R = Et, R' = p-Tol; c, R = Ph, R' = Me. X = BF, PF or BAr) were synthesized. The elongated Ru-Cl bond in the 18ē complexes is shown to dissociate even in apolar solvents to form the corresponding 16ē cations, which can be readily isolated as salts with non-coordinating anions. The coordinatively unsaturated 16ē complexes are stable species due to efficient π-electron donation from the nitrogen atoms of the zwitterionic NPN-ligand. The ruthenium iminophosphonamides are moderately active in the ROMP polymerization of norbornene; the 16ē complexes 4a,b yield high molecular weight polymers (M∼ 300 × 10) with a narrow distribution M/M∼ 1.6, while the 18ē complexes 3a,b give polymers of lower molecular weight (M < 50 × 10) with a wider polydispersity index M/M∼ 2.5.

It was shown that rotational mobility of molecules in crystals is affected by the symmetry of their surroundings. A hypothesis was proposed for the discovered correlation. Three cases are possible for the location of the molecules with respect to the crystallographic symmetry elements: I – the location in a general position; II – the location in special positions without symmetry disordering; III – the location in special positions with symmetry disordering. According to the experimental data, the rotation barrier heights at the location of the molecules in cases I and III are lower than in case II. This fact is explained by the amplitude and phase shifts of the rotational energy profiles of two parts of the molecule in case I and by increasing the number of minima on the rotation barrier profile at disordering the molecules by symmetry in case III. The way is proposed for lowering the rotational barrier of molecules in crystals.