2,2,2-Tris(pyrazolyl)ethoxide (Ep(OX)) ruthenium(II) complexes, (Ep(OX))RuCl(L)(L'): synthesis, structure, and reactivity

Brandon Quillian; Evan E Joslin; T Brent Gunnoe; Michal Sabat; William H Myers

doi:10.1021/ic3024474

2,2,2-Tris(pyrazolyl)ethoxide (Ep(OX)) ruthenium(II) complexes, (Ep(OX))RuCl(L)(L'): synthesis, structure, and reactivity

Inorg Chem. 2013 Jan 18;52(2):1113-21. doi: 10.1021/ic3024474. Epub 2012 Dec 27.

Authors

Brandon Quillian¹, Evan E Joslin, T Brent Gunnoe, Michal Sabat, William H Myers

Affiliation

¹ Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.

PMID: 23270304
DOI: 10.1021/ic3024474

Abstract

Treatment of RuCl(2)(PPh(3))(3) with sodium 2,2,2-tris(pyrazolyl)ethoxide [NaOCH(2)C(pz)(3); pz = pyrazolyl] affords the asymmetric heteroscorpionate complex cis-(Ep(OX))RuCl(PPh(3))(2) (1), (Ep(OX) = κ(3)-N,N,O-OCH(2)C(pz)(3)), which can be converted to Ru(II) compounds (2-6), (Ep(OX))RuCl(L)(L') [(2) L = PPh(3), L' = P(OCH(2))(3)CEt; (3) L = L' = P(OCH(2))(3)CEt; (5) L, L' = PPh(3), CO; (6) L = L' = CO]. Compounds 1 and 3 react with CHCl(3) at 60 and 100 °C, respectively, to yield cationic tris(pyrazolyl)methane Ru(II) complexes, [(κ(3)-N,N,N-Mp)RuCl(L)(2)]Cl [Mp = HC(pz)(3); (7) L = PPh(3); (8) L = P(OCH(2))(3)CEt]. The complexes have been characterized by (1)H, (13)C, and (31)P{(1)H} NMR spectroscopy, elemental analysis, high resolution mass spectrometry, and cyclic voltammetry. Complexes 1 and 3 have also been characterized by single crystal X-ray analysis.