Crystal structure and electronic and magnetic properties of hexacyanoosmate(III)

Pablo Albores; Leonardo D Slep; Luis M Baraldo; Ricardo Baggio; María Teresa Garland; Eva Rentschler

doi:10.1021/ic0516818

Crystal structure and electronic and magnetic properties of hexacyanoosmate(III)

Inorg Chem. 2006 Mar 20;45(6):2361-3. doi: 10.1021/ic0516818.

Authors

Pablo Albores¹, Leonardo D Slep, Luis M Baraldo, Ricardo Baggio, María Teresa Garland, Eva Rentschler

Affiliation

¹ Departamento de Química Inorganica, Analítica y Química Física, INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.

PMID: 16529444
DOI: 10.1021/ic0516818

Abstract

The [Os(III)(CN)6]3- anion is prepared by chemical oxidation in aqueous solution and isolated as yellow prisms of [Ph4P]3[Os(III)(CN)6].6H2O (1). This species crystallizes in the triclinic space group P with cell parameters a = 13.7609(11) A, b = 16.2275(13) A, c = 17.0895(14) A, alpha = 91.4040(10) degrees , beta = 109.3600(10) degrees , gamma = 102.3970(10) degrees , V = 3497.4(5) A(3), and Z = 2. The slightly distorted octahedral moiety displays Os-C and C-N bond lengths that average 2.058 and 1.146 A, respectively. Spin-orbit-coupling splitting of the ground-state term dominates the NIR region of the electronic spectrum and the magnetic behavior of 1. The experimental information points to higher spin delocalization over the coordinated cyanides than in [Fe(III)(CN)6]3-.