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

Malcolm H. Chisholm, Nathan J. Patmore

Research output: Contribution to journalArticle

4 Citations (Scopus)

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.

LanguageEnglish
Pages91-96
Number of pages6
JournalDalton Transactions
Issue number1
Early online date11 Aug 2006
DOIs
Publication statusPublished - 1 Jan 2007
Externally publishedYes

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Tungsten
Molybdenum
Aromatic Hydrocarbons
Oxidation
Toluene
Molecular orbitals
Carbon Monoxide
Ground state
Electronic structure
Density functional theory
Cations
Metals
Acids
Air
tetrahydrofuran

Cite this

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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.",
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2,5-Dianilinoterephthalate bridged MM quadruply bonded complexes of molybdenum and tungsten. / Chisholm, Malcolm H.; Patmore, Nathan J.

In: Dalton Transactions, No. 1, 01.01.2007, p. 91-96.

Research output: Contribution to journalArticle

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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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