Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates

Wolfgang A. Hermann, Werner R. Thiel, Fritz E. Kühn, Richard W. Fischer, Matthias Kleine, Eberhardt Herdtweck, Wolfgang Scherer, J. Mink

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Abstract

Two structural types of perrhenic anhydrides result from treatment of Re2O7 with carboxylic anhydrides (RCO)2O in acetonitrile or tetrahydrofuran solution. Strongly electron-withdrawing groups, cf. R = CF3, thus lead to complexes of type RC(O)-O-ReO3·2L (L = CH3CN, thf) exhibiting η1-coordinated carboxylato groups and octahedral coordination at rhenium(VII), both in solution (IR, 17O NMR) and in the solid state (X-ray crystal structure of CF3C(O)-O-ReO3·2CH3CN (crystal data: space group P21/n (No. 14), a = 10.522(3) Å, b = 8.193(1) Å, c = 13.094(4) Å, β = 90.59(1)°, Z = 4)). Analogous coordination is observed in the X-ray crystal structure of Re2O7·2CH3-CN (space group P21/m (No. 11), a = 5.363(1) Å, b = 11.763(2) Å, c = 8.273(2) Å, β = 94.395(9)°, Z = 2)). By way of contrast, anhydrides of weak carboxylic acids, cf. R = CH3, yield mixed anhydrides of general formula RC(O)-OReO3·L (L = CH3CN, thf), the structures of which compounds display octahedral rhenium(VII) and η2-coordinated carboxylato groups. These structures are again observed in solution and in the solid state (X-ray crystal structure of CH3C(O)-OReO3·CH3CN (space group C2/m (No. 12), a = 14.818(8) Å, b = 6.976(2) Å, c = 7.390(4) Å, β = 94.64(2)°, Z = 4)). As a result of these structural features, only mixed anhydrides containing strongly electron-withdrawing substituents react cleanly with alkyltin compounds to yield the alkylrhenium(VII) oxides of the type alkyl-ReO3.

Original languageEnglish
Pages (from-to)5188-5194
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number23
Publication statusPublished - 1993

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Anhydrides
Chemical elements
Transition metals
anhydrides
reactivity
transition metals
Rhenium
Crystal structure
X rays
rhenium
crystal structure
Electrons
solid state
Carboxylic Acids
x rays
Oxides
tetrahydrofuran
carboxylic acids
acetonitrile
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Hermann, W. A., Thiel, W. R., Kühn, F. E., Fischer, R. W., Kleine, M., Herdtweck, E., ... Mink, J. (1993). Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates. Inorganic Chemistry, 32(23), 5188-5194.

Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates. / Hermann, Wolfgang A.; Thiel, Werner R.; Kühn, Fritz E.; Fischer, Richard W.; Kleine, Matthias; Herdtweck, Eberhardt; Scherer, Wolfgang; Mink, J.

In: Inorganic Chemistry, Vol. 32, No. 23, 1993, p. 5188-5194.

Research output: Contribution to journalArticle

Hermann, WA, Thiel, WR, Kühn, FE, Fischer, RW, Kleine, M, Herdtweck, E, Scherer, W & Mink, J 1993, 'Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates', Inorganic Chemistry, vol. 32, no. 23, pp. 5188-5194.
Hermann WA, Thiel WR, Kühn FE, Fischer RW, Kleine M, Herdtweck E et al. Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates. Inorganic Chemistry. 1993;32(23):5188-5194.
Hermann, Wolfgang A. ; Thiel, Werner R. ; Kühn, Fritz E. ; Fischer, Richard W. ; Kleine, Matthias ; Herdtweck, Eberhardt ; Scherer, Wolfgang ; Mink, J. / Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates. In: Inorganic Chemistry. 1993 ; Vol. 32, No. 23. pp. 5188-5194.
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title = "Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates",
abstract = "Two structural types of perrhenic anhydrides result from treatment of Re2O7 with carboxylic anhydrides (RCO)2O in acetonitrile or tetrahydrofuran solution. Strongly electron-withdrawing groups, cf. R = CF3, thus lead to complexes of type RC(O)-O-ReO3·2L (L = CH3CN, thf) exhibiting η1-coordinated carboxylato groups and octahedral coordination at rhenium(VII), both in solution (IR, 17O NMR) and in the solid state (X-ray crystal structure of CF3C(O)-O-ReO3·2CH3CN (crystal data: space group P21/n (No. 14), a = 10.522(3) {\AA}, b = 8.193(1) {\AA}, c = 13.094(4) {\AA}, β = 90.59(1)°, Z = 4)). Analogous coordination is observed in the X-ray crystal structure of Re2O7·2CH3-CN (space group P21/m (No. 11), a = 5.363(1) {\AA}, b = 11.763(2) {\AA}, c = 8.273(2) {\AA}, β = 94.395(9)°, Z = 2)). By way of contrast, anhydrides of weak carboxylic acids, cf. R = CH3, yield mixed anhydrides of general formula RC(O)-OReO3·L (L = CH3CN, thf), the structures of which compounds display octahedral rhenium(VII) and η2-coordinated carboxylato groups. These structures are again observed in solution and in the solid state (X-ray crystal structure of CH3C(O)-OReO3·CH3CN (space group C2/m (No. 12), a = 14.818(8) {\AA}, b = 6.976(2) {\AA}, c = 7.390(4) {\AA}, β = 94.64(2)°, Z = 4)). As a result of these structural features, only mixed anhydrides containing strongly electron-withdrawing substituents react cleanly with alkyltin compounds to yield the alkylrhenium(VII) oxides of the type alkyl-ReO3.",
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T1 - Multiple bonds between transition metals and main-group elements. 124. Structures and reactivity of acylperrhenates

AU - Hermann, Wolfgang A.

AU - Thiel, Werner R.

AU - Kühn, Fritz E.

AU - Fischer, Richard W.

AU - Kleine, Matthias

AU - Herdtweck, Eberhardt

AU - Scherer, Wolfgang

AU - Mink, J.

PY - 1993

Y1 - 1993

N2 - Two structural types of perrhenic anhydrides result from treatment of Re2O7 with carboxylic anhydrides (RCO)2O in acetonitrile or tetrahydrofuran solution. Strongly electron-withdrawing groups, cf. R = CF3, thus lead to complexes of type RC(O)-O-ReO3·2L (L = CH3CN, thf) exhibiting η1-coordinated carboxylato groups and octahedral coordination at rhenium(VII), both in solution (IR, 17O NMR) and in the solid state (X-ray crystal structure of CF3C(O)-O-ReO3·2CH3CN (crystal data: space group P21/n (No. 14), a = 10.522(3) Å, b = 8.193(1) Å, c = 13.094(4) Å, β = 90.59(1)°, Z = 4)). Analogous coordination is observed in the X-ray crystal structure of Re2O7·2CH3-CN (space group P21/m (No. 11), a = 5.363(1) Å, b = 11.763(2) Å, c = 8.273(2) Å, β = 94.395(9)°, Z = 2)). By way of contrast, anhydrides of weak carboxylic acids, cf. R = CH3, yield mixed anhydrides of general formula RC(O)-OReO3·L (L = CH3CN, thf), the structures of which compounds display octahedral rhenium(VII) and η2-coordinated carboxylato groups. These structures are again observed in solution and in the solid state (X-ray crystal structure of CH3C(O)-OReO3·CH3CN (space group C2/m (No. 12), a = 14.818(8) Å, b = 6.976(2) Å, c = 7.390(4) Å, β = 94.64(2)°, Z = 4)). As a result of these structural features, only mixed anhydrides containing strongly electron-withdrawing substituents react cleanly with alkyltin compounds to yield the alkylrhenium(VII) oxides of the type alkyl-ReO3.

AB - Two structural types of perrhenic anhydrides result from treatment of Re2O7 with carboxylic anhydrides (RCO)2O in acetonitrile or tetrahydrofuran solution. Strongly electron-withdrawing groups, cf. R = CF3, thus lead to complexes of type RC(O)-O-ReO3·2L (L = CH3CN, thf) exhibiting η1-coordinated carboxylato groups and octahedral coordination at rhenium(VII), both in solution (IR, 17O NMR) and in the solid state (X-ray crystal structure of CF3C(O)-O-ReO3·2CH3CN (crystal data: space group P21/n (No. 14), a = 10.522(3) Å, b = 8.193(1) Å, c = 13.094(4) Å, β = 90.59(1)°, Z = 4)). Analogous coordination is observed in the X-ray crystal structure of Re2O7·2CH3-CN (space group P21/m (No. 11), a = 5.363(1) Å, b = 11.763(2) Å, c = 8.273(2) Å, β = 94.395(9)°, Z = 2)). By way of contrast, anhydrides of weak carboxylic acids, cf. R = CH3, yield mixed anhydrides of general formula RC(O)-OReO3·L (L = CH3CN, thf), the structures of which compounds display octahedral rhenium(VII) and η2-coordinated carboxylato groups. These structures are again observed in solution and in the solid state (X-ray crystal structure of CH3C(O)-OReO3·CH3CN (space group C2/m (No. 12), a = 14.818(8) Å, b = 6.976(2) Å, c = 7.390(4) Å, β = 94.64(2)°, Z = 4)). As a result of these structural features, only mixed anhydrides containing strongly electron-withdrawing substituents react cleanly with alkyltin compounds to yield the alkylrhenium(VII) oxides of the type alkyl-ReO3.

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