Synthesis, Structure, and Properties of Asymmetric Benzoyldiazenido and Thiobenzoyldiazenido Complexes of Molybdenum

Michael W. Bishop; Joseph Chatt; J. R. Dilworth; J. R. Hyde; K. Venkatasubramanian; Jon Zubieta; S. Kim

doi:10.1021/ic50188a046

Synthesis, Structure, and Properties of Asymmetric Benzoyldiazenido and Thiobenzoyldiazenido Complexes of Molybdenum

Michael W. Bishop, Joseph Chatt, J. R. Dilworth, J. R. Hyde, K. Venkatasubramanian, Jon Zubieta, S. Kim

Research output: Contribution to journal › Article › peer-review

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Abstract

The synthesis of the compounds of general formula [Mo₂O(S₂CNR)₂(YC₆H₄CXN₂)₂]-Sol, X = S and O, Y = H and Cl, and Sol = CH₂C1₂ and CHC1₃, is reported. The compounds were characterized by elemental analyses and infrared, electronic, and 1H NMR spectroscopy. The 1H NMR spectra exhibited a number of alkyl resonances, suggesting that the dithiocarbamate ligands are nonequivalent. The molecular structures of the compounds [Mo₂O(S₂CNEt₂)₂(C₆H₅CON₂)₂].CH₂Cl2 and [Mo₂O(S₂CNEt₂)₂(ClC₆H₄CSN₂)₂].CHCl₃ were revealed in single-crystal X-ray diffraction studies. The structures are analogous and shown to be asymmetric dinuclear complexes with bridging benzoyldiazendio or thiobenzoyldiazenido ligands. The nonplanar Mo2N2 rhombus is common to both structures and exhibits a nearly identical geometry in the two derivatives. The geometries about the square-pyramidal Mo2 sites are also constant. The Mol sites are approximately trigonal prismatic, the coordination polyhedra constrained by the geometric requirements of sulfur vs. oxygen coordination. Voltammetric studies of the dimers indicate a reversible one-electron reduction, followed by an irreversible cathodic process at more negative potentials. The redox behavior of the dimers is discussed and contrasted with that of the symmetrical dimers Mo2O3(S2CX)4, X = -NR2, -OR, and -SR.

Original language	English (US)
Pages (from-to)	2917-2928
Number of pages	12
Journal	Inorganic Chemistry
Volume	17
Issue number	10
DOIs	https://doi.org/10.1021/ic50188a046
State	Published - 1978
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{8af0749caf694112ba1482cab5e44cf6,

title = "Synthesis, Structure, and Properties of Asymmetric Benzoyldiazenido and Thiobenzoyldiazenido Complexes of Molybdenum",

abstract = "The synthesis of the compounds of general formula [Mo2O(S2CNR)2(YC6H4CXN2)2]-Sol, X = S and O, Y = H and Cl, and Sol = CH2C12 and CHC13, is reported. The compounds were characterized by elemental analyses and infrared, electronic, and 1H NMR spectroscopy. The 1H NMR spectra exhibited a number of alkyl resonances, suggesting that the dithiocarbamate ligands are nonequivalent. The molecular structures of the compounds [Mo2O(S2CNEt2)2(C6H5CON2)2].CH2Cl2 and [Mo2O(S2CNEt2)2(ClC6H4CSN2)2].CHCl3 were revealed in single-crystal X-ray diffraction studies. The structures are analogous and shown to be asymmetric dinuclear complexes with bridging benzoyldiazendio or thiobenzoyldiazenido ligands. The nonplanar Mo2N2 rhombus is common to both structures and exhibits a nearly identical geometry in the two derivatives. The geometries about the square-pyramidal Mo2 sites are also constant. The Mol sites are approximately trigonal prismatic, the coordination polyhedra constrained by the geometric requirements of sulfur vs. oxygen coordination. Voltammetric studies of the dimers indicate a reversible one-electron reduction, followed by an irreversible cathodic process at more negative potentials. The redox behavior of the dimers is discussed and contrasted with that of the symmetrical dimers Mo2O3(S2CX)4, X = -NR2, -OR, and -SR.",

author = "Bishop, {Michael W.} and Joseph Chatt and Dilworth, {J. R.} and Hyde, {J. R.} and K. Venkatasubramanian and Jon Zubieta and S. Kim",

year = "1978",

doi = "10.1021/ic50188a046",

language = "English (US)",

volume = "17",

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journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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T1 - Synthesis, Structure, and Properties of Asymmetric Benzoyldiazenido and Thiobenzoyldiazenido Complexes of Molybdenum

AU - Bishop, Michael W.

AU - Chatt, Joseph

AU - Dilworth, J. R.

AU - Hyde, J. R.

AU - Venkatasubramanian, K.

AU - Zubieta, Jon

AU - Kim, S.

PY - 1978

Y1 - 1978

N2 - The synthesis of the compounds of general formula [Mo2O(S2CNR)2(YC6H4CXN2)2]-Sol, X = S and O, Y = H and Cl, and Sol = CH2C12 and CHC13, is reported. The compounds were characterized by elemental analyses and infrared, electronic, and 1H NMR spectroscopy. The 1H NMR spectra exhibited a number of alkyl resonances, suggesting that the dithiocarbamate ligands are nonequivalent. The molecular structures of the compounds [Mo2O(S2CNEt2)2(C6H5CON2)2].CH2Cl2 and [Mo2O(S2CNEt2)2(ClC6H4CSN2)2].CHCl3 were revealed in single-crystal X-ray diffraction studies. The structures are analogous and shown to be asymmetric dinuclear complexes with bridging benzoyldiazendio or thiobenzoyldiazenido ligands. The nonplanar Mo2N2 rhombus is common to both structures and exhibits a nearly identical geometry in the two derivatives. The geometries about the square-pyramidal Mo2 sites are also constant. The Mol sites are approximately trigonal prismatic, the coordination polyhedra constrained by the geometric requirements of sulfur vs. oxygen coordination. Voltammetric studies of the dimers indicate a reversible one-electron reduction, followed by an irreversible cathodic process at more negative potentials. The redox behavior of the dimers is discussed and contrasted with that of the symmetrical dimers Mo2O3(S2CX)4, X = -NR2, -OR, and -SR.

AB - The synthesis of the compounds of general formula [Mo2O(S2CNR)2(YC6H4CXN2)2]-Sol, X = S and O, Y = H and Cl, and Sol = CH2C12 and CHC13, is reported. The compounds were characterized by elemental analyses and infrared, electronic, and 1H NMR spectroscopy. The 1H NMR spectra exhibited a number of alkyl resonances, suggesting that the dithiocarbamate ligands are nonequivalent. The molecular structures of the compounds [Mo2O(S2CNEt2)2(C6H5CON2)2].CH2Cl2 and [Mo2O(S2CNEt2)2(ClC6H4CSN2)2].CHCl3 were revealed in single-crystal X-ray diffraction studies. The structures are analogous and shown to be asymmetric dinuclear complexes with bridging benzoyldiazendio or thiobenzoyldiazenido ligands. The nonplanar Mo2N2 rhombus is common to both structures and exhibits a nearly identical geometry in the two derivatives. The geometries about the square-pyramidal Mo2 sites are also constant. The Mol sites are approximately trigonal prismatic, the coordination polyhedra constrained by the geometric requirements of sulfur vs. oxygen coordination. Voltammetric studies of the dimers indicate a reversible one-electron reduction, followed by an irreversible cathodic process at more negative potentials. The redox behavior of the dimers is discussed and contrasted with that of the symmetrical dimers Mo2O3(S2CX)4, X = -NR2, -OR, and -SR.

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ER -

Synthesis, Structure, and Properties of Asymmetric Benzoyldiazenido and Thiobenzoyldiazenido Complexes of Molybdenum

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