Synthesis and X-ray studies of ruthenium(II) complexes containing hydrazine and benzyl isocyanide ligands

Abstract

ABSTRACT. The reaction of the polymeric species [{RuCl2(COD)}x] (1 ; x > 2; COD = cyclo-octa-1,5-diene) and hydrazine hydrate in methanol under reflux gave a pale pink solution from which the salt [Ru(COD)(N2H4)4][BPh4]2.CH3OH (2) was isolated on addition of NaBPh4. Treatment of 2 in refluxing acetone in the presence of the ligand benzyl isocyanide give a complex of stoichiometry [Ru(NH2N=CMe2)2(PhCH2NC)4][BPh4]2 (3) on the substitution of the labile COD ligand. The two compounds have been characterized by elemental analyses, IR and NMR measurements and single-crystal X-ray diffraction studies. The ruthenium in both compounds has a distorted octahedral coordination geometry.

The Synthesis and Structure of Hexakis(dimethylphenylphosphonite)ruthenium(II) bis[tetraphenylborate(–1)]

“…Such derivatives of the polymer contain labile hydrazine groups in solution making them ideal precursors for the synthesis of an extensive range of ruthenium(I1) salts 7,9. The most commonly applied among these hydrazine derivatives is the ruthenium(II) hydrazine salt [Ru(COD)(NH 2 NH 2 ) 4 ][BPh 4 ] 2 ( 2 ) and we have recently demonstrated the use of readily available and non‐regulated hydrazine hydrate to produce 2 instead of pure anhydrous hydrazine usually employed in this reaction 10…”

“…In order to study the bonding mode of ligand to metal in the new compound, the IR and the 1 H NMR spectra of both the precursor 2 and those of complex 3 were compared. The complex has a new ν(Ru–P) band at 528 cm –1 ,13 while all the other characteristic IR bands observed in 2 10 were completely absent. The 1 H NMR spectrum of 3 contains a singlet at δ = 3.26 ppm, which was assigned to the protons on the methoxy groups of P(OMe) 2 Ph but lacks the proton resonances of coordinated COD and hydrazine.…”

Preparation of Azine Complexes of Ruthenium(II)

“…The acetonehydrazone ligand shows Ru‐N bond lenghts of 2.1806(14) Å, it is only slightly longer to those found for the three acetonehydrazone ruthenium complexes crystallographically described previously: 2.17 Å for the cation [Ru(NH 2 =NCMe 2 ) 2 {P(OMe) 3 } 4 ] 2+ , 2.121(13) in the anion [(COD)Ru(NH 2 NCMe 2 )(P 3 O 9 )] − , or 2.1416(13) Å in the cation [OsCl(COD)(CN t Bu)(NH 2 N=CMe 2 ) 2 ] 2+ . Also Ru‐N−N and N−N–C angles, 114.13(12) and 114.97(19), are similar to those found in the mentioned complex, about 115 and 116°, respectively.…”