Synthesis and crystal structure of [H₅O₂][Ru(CO)₃Cl₃] · SbCl₃

Abstract

Crystals of [H5O2][Ru(CO)3Cl3] · SbCl3 are triclinic, space group P1, with unit cell of dimensions: a = 7.129(2), b = 10.129(3), c = 10.997(3) Å, α = 75.40(2)°, β = 97.17(2)°; γ = 120.94(2)°. The structure was solved from X‐ray diffractometer data by Patterson and Fourier synthesis and refined by full matrix least‐squares method to R = 3.02% for 3268 independent reflections. The [Ru(CO)3Cl3]− anion has an approximately octahedral fac configuration. The antimony atom has three chlorine neighbours at 2.387(2), 2.364(2) and 2.368(2) Å giving the expected angular conformation and three other neighbours at longer distances completing with the lone pair a monocaped octahedral environment around antimony. The acidic hydrogen has been transfered to two water molecules giving an asymmetric [H5O2]+ ion with a very short hydrogen bond of 2.373(9) Å.

On the Reaction of Phosphorous Acid with Superacids and the Crystal Structure of H5O2+SbF6- and Me4N+HPF5-

“…In these structures, the hydrogen atoms were not determined from difference Fourier syntheses. Further X-ray investigations in this field were carried out by Mootz et al, − and other research groups, − who found the H 5 O 2 + cation to be present in crystalline hydrates of some acids. In these structures (refs −33), the hydrogen atoms were determined from difference Fourier syntheses.…”

Reactions of [Ru(CO)3Cl2]2 with aromatic nitrogen donor ligands in alcoholic media

“…Similar ion pairs have been obtained typically from cluster fragmentation. 40,41 To our knowledge, only one other example of asymmetric cleavage of the [Ru(CO) 3 Cl 2 ] 2 with ion pair as the unique product has been reported. Reaction of C 5 H 5 (Me 3 Si) with [Ru(CO) 3 Cl 2 ] 2 leads to an ion pair of [Ru(CO) 3 42 However, in this case the cyclopentadienyl ligand replaces both chlorides to give a tricarbonyl-Cp complex, whereas in our case just one chloride is replaced.…”