One Step Closer to Structural Models for HDS Catalysts: Thienyl-Oxo Complexes of Re(V)

Philip R. Stafford; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/ic00125a022

One Step Closer to Structural Models for HDS Catalysts: Thienyl-Oxo Complexes of Re(V)

Philip R. Stafford, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

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Abstract

The present investigation focuses on thiophene derivatives of oxometal centers with low d-electron counts. Treatment of a THF slurry of ReOCl₃(PPh₃)₂ with thienyllithium reagents afforded Li(THF)_nReO(thienyl)₄ where thienyl is 2-C₄H₃S, 2-MeC₄H₂,2-C₈H₅S (benzothienyl), and 2-C₁₂H₇S (dibenzothienyl). In contrast to the previously reported low-valent derivatives these species are reactive toward protic and oxidizing reagents. Electrochemical studies demonstrate that these Re^v complexes undergo oxidation at mild potentials. Crystallographic analyses of Li(THF)₃ReO(C₄H₃S)₄ and Li(THF)₄ReO(C₈H₅S)₄ indicate a square pyramidal Re center with the four thienyl ligands tilted in a pinwheel arrangement. Studies on Re(2-C₄H₃S)(CO)₅ reveal that it is stable toward hydrolysis.

Original language	English (US)
Pages (from-to)	5220-5225
Number of pages	6
Journal	Inorganic Chemistry
Volume	34
Issue number	21
DOIs	https://doi.org/10.1021/ic00125a022
State	Published - Oct 1 1995

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00125a022

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title = "One Step Closer to Structural Models for HDS Catalysts: Thienyl-Oxo Complexes of Re(V)",

abstract = "The present investigation focuses on thiophene derivatives of oxometal centers with low d-electron counts. Treatment of a THF slurry of ReOCl3(PPh3)2 with thienyllithium reagents afforded Li(THF)nReO(thienyl)4 where thienyl is 2-C4H3S, 2-MeC4H2,2-C8H5S (benzothienyl), and 2-C12H7S (dibenzothienyl). In contrast to the previously reported low-valent derivatives these species are reactive toward protic and oxidizing reagents. Electrochemical studies demonstrate that these Rev complexes undergo oxidation at mild potentials. Crystallographic analyses of Li(THF)3ReO(C4H3S)4 and Li(THF)4ReO(C8H5S)4 indicate a square pyramidal Re center with the four thienyl ligands tilted in a pinwheel arrangement. Studies on Re(2-C4H3S)(CO)5 reveal that it is stable toward hydrolysis.",

author = "Stafford, {Philip R.} and Rauchfuss, {Thomas B.} and Wilson, {Scott R.}",

year = "1995",

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journal = "Inorganic Chemistry",

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T2 - Thienyl-Oxo Complexes of Re(V)

AU - Stafford, Philip R.

AU - Rauchfuss, Thomas B.

AU - Wilson, Scott R.

PY - 1995/10/1

Y1 - 1995/10/1

N2 - The present investigation focuses on thiophene derivatives of oxometal centers with low d-electron counts. Treatment of a THF slurry of ReOCl3(PPh3)2 with thienyllithium reagents afforded Li(THF)nReO(thienyl)4 where thienyl is 2-C4H3S, 2-MeC4H2,2-C8H5S (benzothienyl), and 2-C12H7S (dibenzothienyl). In contrast to the previously reported low-valent derivatives these species are reactive toward protic and oxidizing reagents. Electrochemical studies demonstrate that these Rev complexes undergo oxidation at mild potentials. Crystallographic analyses of Li(THF)3ReO(C4H3S)4 and Li(THF)4ReO(C8H5S)4 indicate a square pyramidal Re center with the four thienyl ligands tilted in a pinwheel arrangement. Studies on Re(2-C4H3S)(CO)5 reveal that it is stable toward hydrolysis.

AB - The present investigation focuses on thiophene derivatives of oxometal centers with low d-electron counts. Treatment of a THF slurry of ReOCl3(PPh3)2 with thienyllithium reagents afforded Li(THF)nReO(thienyl)4 where thienyl is 2-C4H3S, 2-MeC4H2,2-C8H5S (benzothienyl), and 2-C12H7S (dibenzothienyl). In contrast to the previously reported low-valent derivatives these species are reactive toward protic and oxidizing reagents. Electrochemical studies demonstrate that these Rev complexes undergo oxidation at mild potentials. Crystallographic analyses of Li(THF)3ReO(C4H3S)4 and Li(THF)4ReO(C8H5S)4 indicate a square pyramidal Re center with the four thienyl ligands tilted in a pinwheel arrangement. Studies on Re(2-C4H3S)(CO)5 reveal that it is stable toward hydrolysis.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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One Step Closer to Structural Models for HDS Catalysts: Thienyl-Oxo Complexes of Re(V)

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