Synthesis and structures of Dioxoruthenium(VI) complexes. Oxo transfer from trans-O2Ru(py)2(O2CR)2

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Original languageEnglish
Pages (from-to)4190-4195
Journal / PublicationInorganic Chemistry
Volume29
Issue number21
Publication statusPublished - 1 Oct 1990
Externally publishedYes

Abstract

The direct synthesis of a series of dioxoruthenium(VI) complexes O2Ru(py)2(O2CR)2 with R = CH3, CH3CH2, CH3CH2CH2, (CH3)2CH, and C6H5 is carried out in one step from the readily available, but highly insoluble, barium ruthenate. X-ray crystallography of O2Ru(py)2(O2CCH3)2: space group P1 (triclinic) with lattice constants a = 8.359 (2) Å, b = 9.599 (4) Å, c = 13.431 (8) Å, α = 89.68 (5)°, β = 74.20 (5)°, γ = 69.52 (3)°, and Z = 2. This establishes the linear trans-dioxo functionality with a pair of trans-pyridine and trans-acetato ligands to complete the octahedral coordination. The relatively long O=Ru bond length of 1.726 (1) Å is discussed in terms of the oxidative reactivity of these dioxoruthenium(VI) complexes toward oxygen atom transfer to various substrates including phosphines, olefins, phenols, alkanes, and ethers - especially with regard to the competitive insertion into C=C and saturated C-H bonds of olefins. © 1990 American Chemical Society.