Structure of tetra-n-butyratodiruthenium chloride, a compound with a strong metal-metal bond

Abstract

The crystal and molecular structures of tetra-»-butyratodiruthenium chloride, R^CCbCCsI+hCl, have been determined using the intensities of 708 independent, statistically significant reflections collected with a counter diffract uneter. The compound crystallizes in the tetragonal space group I42d with unit cell dimensions a = 13.265 ± 0.005 A and c -24.453 ± 0.008 A (Pobsd = 1.76 ± 0.03 g cm-3 and poaiod = 1.81 g cm-3 forZ = 8). The structure, excluding hydrogen atoms, was solved using Patterson and Fourier methods and refined by full-matrix least-squares methods to a conventional unweighted residual of 7.3%. The compound contains the dinuclear, carboxylate-bridged species Ru2(02CC3H7)4 +with a very short Ru-Ru distance of 2.281 Á. This short bond length and the reported presence of three unpaired electrons on the cation may be rationalized in terms of molecular orbital theory. The two ruthenium atoms of a given molecule are equivalent by virtue of a crystallographic twofold axis and therefore, barring disorder, for which we find no evidence, exist in thé common, nonintegral oxidation state of +2.5. Chloride ions bridge adjacent dinuclear cations in the crystal to form infinite zigzag chains parallel to the a and b crystallographic axes.

Fluorosulfates of the noble metals. Part 6. Synthesis and magnetic properties of fluorosulfato compounds of ruthenium

“…Likewise a binuclear structure, similar to the structure of Ru? (O~CCH~)~CI (18), with a Ru2(SOiF)., core and two terminally bonded -OS02F groups would either be more strongly paramagnetic, assuming a triplet ground state, or show a more pronounced temperature dependence of x',"", if a singlet-triplet equilibrium is encountered. For the very same reason, the lack of temperature dependence rules out a possible phase equilibrium between a diamagnetic and a paramagnetic form.…”

Complexation of Tetrakis(acetato)chloridodiruthenium with Naphthyridine‐2,7‐dicarboxylate – Characterization and Catalytic Activity

“…Owing to unique metal-metal interactions between the mixed-valence ruthenium ions, tetrakis(acetato)chloridodiruthenium, Ru 2 (OAc) 4 Cl, [1] and related coordination compounds represent an important class of dimetallic complexes, which have drawn much attention in many aspects including coordination studies [2][3][4] and biological, [5] materials, [6] and catalysis applications. [7] The diruthenium centers of Ru 2 (OAc) 4 Cl are coordinated to four carboxylate groups to form a paddle-wheel shape and are linked by the axial chloride ligand into a polymeric chain.…”

“…Thus, the axial ligands dramatically affect the electronic, spectroscopic, electrochemical, and magnetic properties. [1][2][3][4][5][6][7][8][9] Furthermore, there are many reports concerning the electronic structures of the diruthenium cores, including "Ru 2 + with two and three unpaired electrons, respectively. [9] The replacement of the bridging carboxylate ligands with other multidentate ligands to modify the properties of the resulting complexes is another interesting subject in this area of research.…”

Structure cristalline de Ni(CH3COS)2.2C5H5N

“…La similitude des propri6t6s des compos6s du type Ni(RCOS)2.0,5C2HsOH avec R=CHa ou C6H5 a conduit Melson, Crawford & Geddes (1970) 5. proposer pour Ni(CH3COS)E.0,5CzHsOH une structure semblable 5. celle de Ni(C6HsCOS)z.0,5CzHsOH (Melson, Greene & Bryan, 1970). Les quatre groupements thiocarboxyliques se comporteraient comme des ligands pontant entre deux ions nickel pour former un dim~re comme dans plusieurs carboxylates de m6taux de transition (Bennett, Caulton & Cotton, 1969).…”