Tungsten oxo salicylate complexes from tungsten hexachloride reactions systems

V. Kolesnichenko; M. H. Mason; J. B. Botts; A. M. Botts; T. E. Baroni; J. A. Heppert; A. Rheingold; L. Liable-Sands; G. P.A. Yap

doi:10.1021/ic001456k

Tungsten oxo salicylate complexes from tungsten hexachloride reactions systems

V. Kolesnichenko, M. H. Mason, J. B. Botts, A. M. Botts, T. E. Baroni, J. A. Heppert, A. Rheingold, L. Liable-Sands, G. P.A. Yap

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Abstract

Tungsten hexachloride is a potent halogen-transfer agent, capable of reacting directly with salicylic acid to generate a tungsten oxo fragment and salicoyl chloride. As a result, oxo complexes dominate the chemistry of tungsten-(VI) salicylates. Both mono- and disalicylate substituted tungsten oxo complexes are accessible. The Brønsted free acid W(=O)Cl(Hsal)(sal) complex is a sparingly soluble, presumably polymeric material that can be dissolved in THF. The THF adduct has been characterized by NMR spectroscopy, although an X-ray crystallographic study indicates that the product cocrystallizes with a structurally analogous d¹ WCl₂(Hsal·THF)(sal) byproduct. The remaining chloride ligand in W(=O)Cl(Hsal)(sal) is replaced by a bridging oxo unit when the reaction contains a significant excess of salicylic acid. The product "linear" oxo bridged ditungsten complex, [W(=O)(Hsal)-(sal)]₂O, forms intramolecular hydrogen bonds, accounting for its high solubility in noncoordinating solvents. An X-ray study shows that the intramolecular Hsal·sal hydrogen bonding in this complex accommodates a more linear W-O-W arrangement than does a previously observed class of isostructural diolate derivatives. Tungsten oxo tetrachloride, formed in the initial reaction between salicylic acid and WCl₆, also reacts with the salicoyl chloride byproduct to generate tungsten salicoylate (OAr-2-COCl) complexes.

Original language	English
Pages (from-to)	5010-5016
Number of pages	7
Journal	Inorganic Chemistry
Volume	40
Issue number	19
DOIs	https://doi.org/10.1021/ic001456k
State	Published - Sep 10 2001

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title = "Tungsten oxo salicylate complexes from tungsten hexachloride reactions systems",

abstract = "Tungsten hexachloride is a potent halogen-transfer agent, capable of reacting directly with salicylic acid to generate a tungsten oxo fragment and salicoyl chloride. As a result, oxo complexes dominate the chemistry of tungsten-(VI) salicylates. Both mono- and disalicylate substituted tungsten oxo complexes are accessible. The Br{\o}nsted free acid W(=O)Cl(Hsal)(sal) complex is a sparingly soluble, presumably polymeric material that can be dissolved in THF. The THF adduct has been characterized by NMR spectroscopy, although an X-ray crystallographic study indicates that the product cocrystallizes with a structurally analogous d1 WCl2(Hsal·THF)(sal) byproduct. The remaining chloride ligand in W(=O)Cl(Hsal)(sal) is replaced by a bridging oxo unit when the reaction contains a significant excess of salicylic acid. The product {"}linear{"} oxo bridged ditungsten complex, [W(=O)(Hsal)-(sal)]2O, forms intramolecular hydrogen bonds, accounting for its high solubility in noncoordinating solvents. An X-ray study shows that the intramolecular Hsal·sal hydrogen bonding in this complex accommodates a more linear W-O-W arrangement than does a previously observed class of isostructural diolate derivatives. Tungsten oxo tetrachloride, formed in the initial reaction between salicylic acid and WCl6, also reacts with the salicoyl chloride byproduct to generate tungsten salicoylate (OAr-2-COCl) complexes.",

author = "V. Kolesnichenko and Mason, {M. H.} and Botts, {J. B.} and Botts, {A. M.} and Baroni, {T. E.} and Heppert, {J. A.} and A. Rheingold and L. Liable-Sands and Yap, {G. P.A.}",

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AU - Kolesnichenko, V.

AU - Mason, M. H.

AU - Botts, J. B.

AU - Botts, A. M.

AU - Baroni, T. E.

AU - Heppert, J. A.

AU - Rheingold, A.

AU - Liable-Sands, L.

AU - Yap, G. P.A.

PY - 2001/9/10

Y1 - 2001/9/10

N2 - Tungsten hexachloride is a potent halogen-transfer agent, capable of reacting directly with salicylic acid to generate a tungsten oxo fragment and salicoyl chloride. As a result, oxo complexes dominate the chemistry of tungsten-(VI) salicylates. Both mono- and disalicylate substituted tungsten oxo complexes are accessible. The Brønsted free acid W(=O)Cl(Hsal)(sal) complex is a sparingly soluble, presumably polymeric material that can be dissolved in THF. The THF adduct has been characterized by NMR spectroscopy, although an X-ray crystallographic study indicates that the product cocrystallizes with a structurally analogous d1 WCl2(Hsal·THF)(sal) byproduct. The remaining chloride ligand in W(=O)Cl(Hsal)(sal) is replaced by a bridging oxo unit when the reaction contains a significant excess of salicylic acid. The product "linear" oxo bridged ditungsten complex, [W(=O)(Hsal)-(sal)]2O, forms intramolecular hydrogen bonds, accounting for its high solubility in noncoordinating solvents. An X-ray study shows that the intramolecular Hsal·sal hydrogen bonding in this complex accommodates a more linear W-O-W arrangement than does a previously observed class of isostructural diolate derivatives. Tungsten oxo tetrachloride, formed in the initial reaction between salicylic acid and WCl6, also reacts with the salicoyl chloride byproduct to generate tungsten salicoylate (OAr-2-COCl) complexes.

AB - Tungsten hexachloride is a potent halogen-transfer agent, capable of reacting directly with salicylic acid to generate a tungsten oxo fragment and salicoyl chloride. As a result, oxo complexes dominate the chemistry of tungsten-(VI) salicylates. Both mono- and disalicylate substituted tungsten oxo complexes are accessible. The Brønsted free acid W(=O)Cl(Hsal)(sal) complex is a sparingly soluble, presumably polymeric material that can be dissolved in THF. The THF adduct has been characterized by NMR spectroscopy, although an X-ray crystallographic study indicates that the product cocrystallizes with a structurally analogous d1 WCl2(Hsal·THF)(sal) byproduct. The remaining chloride ligand in W(=O)Cl(Hsal)(sal) is replaced by a bridging oxo unit when the reaction contains a significant excess of salicylic acid. The product "linear" oxo bridged ditungsten complex, [W(=O)(Hsal)-(sal)]2O, forms intramolecular hydrogen bonds, accounting for its high solubility in noncoordinating solvents. An X-ray study shows that the intramolecular Hsal·sal hydrogen bonding in this complex accommodates a more linear W-O-W arrangement than does a previously observed class of isostructural diolate derivatives. Tungsten oxo tetrachloride, formed in the initial reaction between salicylic acid and WCl6, also reacts with the salicoyl chloride byproduct to generate tungsten salicoylate (OAr-2-COCl) complexes.

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U2 - 10.1021/ic001456k

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SP - 5010

EP - 5016

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -

Tungsten oxo salicylate complexes from tungsten hexachloride reactions systems

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