Synthesis and Reactivity of Catecholate Complexes Containing Quadruply Bonded Metal Ions

Jason Christ; Corinne Epps; Victoria Pritchard; Derek Schmeh; Cortlandt Pierpont; Ebbe Nordlander

doi:10.1021/ic902328m

Synthesis and Reactivity of Catecholate Complexes Containing Quadruply Bonded Metal Ions

Jason Christ, Corinne Epps, Victoria Pritchard, Derek Schmeh, Cortlandt Pierpont, Ebbe Nordlander

Chemical Physics

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

Abstract

Quadruply bonded metal complexes of rhenium and molybdenum have been prepared with tetrachlorocatechol. Structural characterization on the [Re-2(Cl(4)Cat)(4)](2-) anion has shown that it consists of distorted square-planar Re(Cl(4)Cat)(2) units linked by a short (2.2067 angstrom) quadruple Re-Re bond. The addition of tetrachlorocatechol to molybdenum acetate was used to prepare the isoelectronic molybdenum analogue "[Mo-2(Cl(4)Cat)(4)](4-)". This complex was found to be far more reactive than the rhenium dimer. A dimer containing a Mo-Mo double bond, [(Cl(4)Cat)(2)Mo(mu-O)(mu-OCH3)Mo(Cl(4)Cat)(2)](3-), was obtained as the methanolysis product of the complex formed initially, and the oxomolybdenum(V) monomer [MoO(Cl(4)Cat)(2)](-) was formed under more oxidative conditions. Both complexes are oxygen-sensitive, giving [MoO2(Cl(4)Cat)(2)](2-) as the final air-stable complex product.

Original language	English
Pages (from-to)	2029-2031
Journal	Inorganic Chemistry
Volume	49
Issue number	5
DOIs	https://doi.org/10.1021/ic902328m
Publication status	Published - 2010

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Chemical Physics (S) (011001060)

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Atom and Molecular Physics and Optics

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title = "Synthesis and Reactivity of Catecholate Complexes Containing Quadruply Bonded Metal Ions",

abstract = "Quadruply bonded metal complexes of rhenium and molybdenum have been prepared with tetrachlorocatechol. Structural characterization on the [Re-2(Cl(4)Cat)(4)](2-) anion has shown that it consists of distorted square-planar Re(Cl(4)Cat)(2) units linked by a short (2.2067 angstrom) quadruple Re-Re bond. The addition of tetrachlorocatechol to molybdenum acetate was used to prepare the isoelectronic molybdenum analogue {"}[Mo-2(Cl(4)Cat)(4)](4-){"}. This complex was found to be far more reactive than the rhenium dimer. A dimer containing a Mo-Mo double bond, [(Cl(4)Cat)(2)Mo(mu-O)(mu-OCH3)Mo(Cl(4)Cat)(2)](3-), was obtained as the methanolysis product of the complex formed initially, and the oxomolybdenum(V) monomer [MoO(Cl(4)Cat)(2)](-) was formed under more oxidative conditions. Both complexes are oxygen-sensitive, giving [MoO2(Cl(4)Cat)(2)](2-) as the final air-stable complex product.",

author = "Jason Christ and Corinne Epps and Victoria Pritchard and Derek Schmeh and Cortlandt Pierpont and Ebbe Nordlander",

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AU - Epps, Corinne

AU - Pritchard, Victoria

AU - Schmeh, Derek

AU - Pierpont, Cortlandt

AU - Nordlander, Ebbe

N1 - The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)

PY - 2010

Y1 - 2010

N2 - Quadruply bonded metal complexes of rhenium and molybdenum have been prepared with tetrachlorocatechol. Structural characterization on the [Re-2(Cl(4)Cat)(4)](2-) anion has shown that it consists of distorted square-planar Re(Cl(4)Cat)(2) units linked by a short (2.2067 angstrom) quadruple Re-Re bond. The addition of tetrachlorocatechol to molybdenum acetate was used to prepare the isoelectronic molybdenum analogue "[Mo-2(Cl(4)Cat)(4)](4-)". This complex was found to be far more reactive than the rhenium dimer. A dimer containing a Mo-Mo double bond, [(Cl(4)Cat)(2)Mo(mu-O)(mu-OCH3)Mo(Cl(4)Cat)(2)](3-), was obtained as the methanolysis product of the complex formed initially, and the oxomolybdenum(V) monomer [MoO(Cl(4)Cat)(2)](-) was formed under more oxidative conditions. Both complexes are oxygen-sensitive, giving [MoO2(Cl(4)Cat)(2)](2-) as the final air-stable complex product.

AB - Quadruply bonded metal complexes of rhenium and molybdenum have been prepared with tetrachlorocatechol. Structural characterization on the [Re-2(Cl(4)Cat)(4)](2-) anion has shown that it consists of distorted square-planar Re(Cl(4)Cat)(2) units linked by a short (2.2067 angstrom) quadruple Re-Re bond. The addition of tetrachlorocatechol to molybdenum acetate was used to prepare the isoelectronic molybdenum analogue "[Mo-2(Cl(4)Cat)(4)](4-)". This complex was found to be far more reactive than the rhenium dimer. A dimer containing a Mo-Mo double bond, [(Cl(4)Cat)(2)Mo(mu-O)(mu-OCH3)Mo(Cl(4)Cat)(2)](3-), was obtained as the methanolysis product of the complex formed initially, and the oxomolybdenum(V) monomer [MoO(Cl(4)Cat)(2)](-) was formed under more oxidative conditions. Both complexes are oxygen-sensitive, giving [MoO2(Cl(4)Cat)(2)](2-) as the final air-stable complex product.

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U2 - 10.1021/ic902328m

DO - 10.1021/ic902328m

M3 - Article

C2 - 20112917

SN - 1520-510X

VL - 49

SP - 2029

EP - 2031

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

Synthesis and Reactivity of Catecholate Complexes Containing Quadruply Bonded Metal Ions

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