Structural Features of Monomeric Octahedral d 2-Rhenium(V) Monooxo Complexes with Oxygen Atoms of Tridentate Chelating (O,N,S) Ligands

The structural features of 31 mononuclear octahedral d2-Re(V) monooxo complexes with tridentate chelating (O,N,S) ligands, [ReO\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left( {{\text{L}}_{{{\text{tri}}}}^{m}} \right)$$\end{document}\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left( {{\text{L}}_{{{\text{bi}}}}^{n}} \right)$$\end{document}] and [ReO\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left( {{\text{L}}_{{{\text{tri}}}}^{m}} \right)$$\end{document}(Lmono)2] (Lmono = Cl, Br, OMe, OPPh3, PPh3) are considered. The Re–O\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${{\left( {{\text{L}}_{{{\text{tri}}}}^{m}} \right)}_{{trans}}}{\kern 1pt} ,$$\end{document} Re–O\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${{\left( {{\text{L}}_{{{\text{bi}}}}^{n}} \right)}_{{trans}}}{\kern 1pt} ,$$\end{document} and Re–O(OMe) bonds in 14 complexes were found to be commensurable in length with (or shorter than) analogous cis-bonds. This indicates the presence of pseudo-dioxo ReO2 groups in these structures with increased orders of both Re–O bonds located in trans-positions relative to each other. In the structures of 12 compounds, the Re–O(Ltri)trans, Re–O(Lbi)trans, and Re–O(OPPh3) bonds are markedly longer than analogous cis-bonds in accordance with the structural consequences of the trans-effect of a multiply bonded oxo ligand.