Cyclopentadienyl nitrosyl compounds of chromium: aqueous solution chemistry, π bonding and nitric oxide loss 

Abstract

The complex [Cr(η-C₅H₅)(NO)₂(CF₃SO ₃)] 1 was synthesised in order to explore the relationship between π-donor ligands and nitrosyl lability and to investigate the aqueous chemistry of the [Cr(η-C₅H₅)(NO)₂]⁺ fragment. Treatment of 1 with σ-donor ligands gave [Cr(η-C₅H₅)(NO)₂(L)][CF₃ SO₃] salts. Potentiometric titrations and ¹H NMR spectroscopic studies of 1 provided evidence for the existence of [Cr(η-C₅H₅)(NO)₂(H₂O)] ⁺ and [Cr(η-C₅H₅)(NO)₂(OH)] in aqueous solution. When generated in situ, [Cr(η-C₅H₅)(NO)₂(OH)] reacted with acetylacetone, pyridinecarboxylic acid, or salicylaldehyde to form paramagnetic, mononitrosyl complexes, which were independently synthesised from the mononitrosyl precursor [Cr(η-C₅H₅)(NO)(µ-I)]₂. The solid-state molecular structures of [Cr(η-C₅Me₅)(NO)₂(CF₃ SO₃)] 2, [Cr(η-C₅H₅)(NO)₂(N₂C ₅H₇)] 9 and [Cr(η-C₅H₅)(NO)(O₂C₅H ₇)] 10 were determined by X-ray crystallography. Crystals of 2 are monoclinic, a = 8.575(1), b = 8.642(1), c = 21.8626(9) Å, β = 91.760(7)°, Z = 4, space group P2₁/n; crystals of 9 are monoclinic, a = 18.3382(4), b = 11.1774(3), c = 12.9102(1) Å, β = 121.386(1)°, Z = 8, space group C2/c; and those of 10 are orthorhombic, a = 17.373(2), b = 8.833(1), c = 6.926(2) Å, Z = 4, space group Pnma.

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