2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten

Malcolm H. Chisholm; Nathan J. Patmore

doi:10.1039/b607709a

2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten

Malcolm H. Chisholm, Nathan J. Patmore

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6 Citations (Scopus)

Abstract

From the reactions between 2,5-dianilinoterephthalic acid and M ₂(O₂CBu^t)₄ in toluene the dicarboxylate bridged complexes [(Bu^tCO₂) ₃M₂]₂{-1,4-(CO₂)₂-2,5- (NHPh)₂C₆H₂}, 1 (M = Mo) and 2 (M = W) have been isolated. The compounds are air sensitive, sparingly soluble in aromatic hydrocarbons but appreciably soluble in tetrahydrofuran. Electronic structure calculations employing density functional theory on the model compounds [(HCO₂)₃M₂]₂{-1,4-(CO ₂)₂-2,5-(NHPh)₂C₆H₂}, indicate that the ground state structure contains a planar bridge and that for molybdenum the HOMO is a bridge based molecular orbital. However, the compounds show reversible oxidation waves (CV and DPV) that for both M = Mo and W are metal based oxidations. Furthermore, the cations 1⁺ and 2⁺ are shown to be valence trapped and fully delocalized respectively. The magnitude of the electronic coupling of the two M₂ centers, H _ab, can be estimated as 383 cm^-1 for 1⁺ and 1500 cm^-1 for 2⁺ based on the corresponding low energy IVCT or charge resonance bands.

Original language	English
Pages (from-to)	91-96
Number of pages	6
Journal	Dalton Transactions
Issue number	1
Early online date	11 Aug 2006
DOIs	https://doi.org/10.1039/b607709a
Publication status	Published - 1 Jan 2007
Externally published	Yes

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title = "2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten",

abstract = "From the reactions between 2,5-dianilinoterephthalic acid and M 2(O2CBut)4 in toluene the dicarboxylate bridged complexes [(ButCO2) 3M2]2{-1,4-(CO2)2-2,5- (NHPh)2C6H2}, 1 (M = Mo) and 2 (M = W) have been isolated. The compounds are air sensitive, sparingly soluble in aromatic hydrocarbons but appreciably soluble in tetrahydrofuran. Electronic structure calculations employing density functional theory on the model compounds [(HCO2)3M2]2{-1,4-(CO 2)2-2,5-(NHPh)2C6H2}, indicate that the ground state structure contains a planar bridge and that for molybdenum the HOMO is a bridge based molecular orbital. However, the compounds show reversible oxidation waves (CV and DPV) that for both M = Mo and W are metal based oxidations. Furthermore, the cations 1+ and 2+ are shown to be valence trapped and fully delocalized respectively. The magnitude of the electronic coupling of the two M2 centers, H ab, can be estimated as 383 cm-1 for 1+ and 1500 cm-1 for 2+ based on the corresponding low energy IVCT or charge resonance bands.",

author = "Chisholm, {Malcolm H.} and Patmore, {Nathan J.}",

year = "2007",

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doi = "10.1039/b607709a",

language = "English",

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journal = "Dalton Transactions",

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T1 - 2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten

AU - Chisholm, Malcolm H.

AU - Patmore, Nathan J.

PY - 2007/1/1

Y1 - 2007/1/1

N2 - From the reactions between 2,5-dianilinoterephthalic acid and M 2(O2CBut)4 in toluene the dicarboxylate bridged complexes [(ButCO2) 3M2]2{-1,4-(CO2)2-2,5- (NHPh)2C6H2}, 1 (M = Mo) and 2 (M = W) have been isolated. The compounds are air sensitive, sparingly soluble in aromatic hydrocarbons but appreciably soluble in tetrahydrofuran. Electronic structure calculations employing density functional theory on the model compounds [(HCO2)3M2]2{-1,4-(CO 2)2-2,5-(NHPh)2C6H2}, indicate that the ground state structure contains a planar bridge and that for molybdenum the HOMO is a bridge based molecular orbital. However, the compounds show reversible oxidation waves (CV and DPV) that for both M = Mo and W are metal based oxidations. Furthermore, the cations 1+ and 2+ are shown to be valence trapped and fully delocalized respectively. The magnitude of the electronic coupling of the two M2 centers, H ab, can be estimated as 383 cm-1 for 1+ and 1500 cm-1 for 2+ based on the corresponding low energy IVCT or charge resonance bands.

AB - From the reactions between 2,5-dianilinoterephthalic acid and M 2(O2CBut)4 in toluene the dicarboxylate bridged complexes [(ButCO2) 3M2]2{-1,4-(CO2)2-2,5- (NHPh)2C6H2}, 1 (M = Mo) and 2 (M = W) have been isolated. The compounds are air sensitive, sparingly soluble in aromatic hydrocarbons but appreciably soluble in tetrahydrofuran. Electronic structure calculations employing density functional theory on the model compounds [(HCO2)3M2]2{-1,4-(CO 2)2-2,5-(NHPh)2C6H2}, indicate that the ground state structure contains a planar bridge and that for molybdenum the HOMO is a bridge based molecular orbital. However, the compounds show reversible oxidation waves (CV and DPV) that for both M = Mo and W are metal based oxidations. Furthermore, the cations 1+ and 2+ are shown to be valence trapped and fully delocalized respectively. The magnitude of the electronic coupling of the two M2 centers, H ab, can be estimated as 383 cm-1 for 1+ and 1500 cm-1 for 2+ based on the corresponding low energy IVCT or charge resonance bands.

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2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten

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