Cyclopentadienyl ruthenium complexes. Part III. Reactivity of some η⁵-cyclopentadienylbis(triphenylphosphine)ruthenium(II) complexes with nitrosyl tribromide and dinitrogen trioxide

Abstract

Mixed ruthenium(II) nitrosyls have been synthesized in yields larger than 60% by a general reaction of [Ru(η5-C5H5)(PPh3)L]+X− (L = 2,2′-bipyridine or 1,10-phenanthroline, X = Cl or Br) or [Ru(η5-C5,H5)(PPh3)(L)X] (L = PPh3, pyridine, 3-picoline, 4-picoline, [Formula: see text], or [Formula: see text]; X− = Cl−, Br−, I−, CN−, NCS−, H−, or SnCl3−) with NOBr3 and N2O3. In these complexes NO seems to bind with the metal ion as NO+. The reactions of N2O3 gave either nitrito or nitrosyl dinitrito complexes. The reactions of NOBr3 with trichlorostannate complexes did not yield nitrosyl complexes, instead nitrito complexes were isolated in which spectroscopic evidence (ir, 1H nmr) suggest π-interaction of one of the phenyl rings of the triphenylphosphine ligand to the ruthenium center. All products are characterised by elementary microanalyses, conductivity, magnetic moment measurements, electronic, ir, and 1H nmr spectral data.

Preparation and Structural Characterization of [CpRu(1,10‐phenanthroline)(CH3CN)][X] and Precursor Complexes (X=PF6, BArF, TRISPHAT‐N)

“…[1][2][3][4][5][6][7] In fact, the CpRu fragment, and its Cp*Ru analogue, are recognized as effective catalysts for the promotion of many versatile synthetic transformations. [4,5,[8][9][10][11][12] Of importance for the current study, combinations of [CpRu] and nitrogenbased ligands [1,3,13,14] such as diimines [15][16][17][18][19][20][21][22][23][24][25][26] were also found to catalyze original processes. [7,27,28] For example, [CpRu(CH 3 CN) 3 ][PF 6 ] and pyridine-imine/pyridine-oxazoline ligands are effective catalysts in enantioselective decarboxylative rearrangements of allylic β-ketoesters and carbonates.…”