title: Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives.
abstract: The reaction between Os(2)(OAc)(4)Cl(2) and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in an Os(III)(2) compound, Os(2)(ap)(4)Cl(2) (1), that can be crystallized as either the cis-(2,2) isomer from a CH(3)OH-CH(2)Cl(2) solution or the (3,1) isomer from a hexanes-CH(2)Cl(2) solution. Compound 1 undergoes facile reactions with LiC(2)Y to yield a series of Os(2)(ap)(4)(C(2)Y)(2) compounds with Y as Ph (2), ferrocenyl (3), SiMe(3) (4), and C(2)SiMe(3) (5). X-ray diffraction study of compound 2 reveals solvent-dependent isomerism similar to that of the parent compound 1. Compound 1 has Os-Os distances of 2.3937(8) and 2.3913(8) Angstroms for the cis-(2,2) and (3,1) isomers, respectively, and is paramagnetic (S = 1). Both the ethynyl derivatives 2-4 and butadiynyl derivative 5 are diamagnetic and have Os-Os distances of 2.456(1), 2.471(1), and 2.481(1) Angstroms for the cis-(2,2) and (3,1) isomers of 2 and (3,1) isomer of 4, respectively. Compounds 1-5 exhibit multiple one-electron redox couples in their cyclic voltammograms, including a reversible Os(2)(8+/7+) couple for 2. Resonance Raman spectra of both compounds 1 and 2 are reported.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33146, USA.
authors.forename: Yan-Hui
authors.initials: YH
authors.lastname: Shi
authors.forename: Wei-Zhong
authors.initials: WZ
authors.lastname: Chen
authors.forename: Kevin D
authors.initials: KD
authors.lastname: John
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Da Re
authors.forename: Joshua L
authors.initials: JL
authors.lastname: Cohn
authors.forename: Guo-Lin
authors.initials: GL
authors.lastname: Xu
authors.forename: Judith L
authors.initials: JL
authors.lastname: Eglin
authors.forename: Alfred P
authors.initials: AP
authors.lastname: Sattelberger
authors.forename: Curtis R
authors.initials: CR
authors.lastname: Hare
authors.forename: Tong
authors.initials: T
authors.lastname: Ren