Naked (C5Me5)2M Cations (M = Sc, Ti, and V) and Their Fluoroarene Complexes
The ionic metallocene complexes [Cp*2M][BPh4] (Cp* = C5Me5) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each...
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Published in | Journal of the American Chemical Society Vol. 127; no. 41; pp. 14310 - 14319 |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
19.10.2005
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Subjects | |
Online Access | Get full text |
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Summary: | The ionic metallocene complexes [Cp*2M][BPh4] (Cp* = C5Me5) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contain one strongly distorted Cp* ligand, with one (V) or two (Ti) agostic C−H···M interactions involving the Cp*Me groups. For Sc and Ti, these Lewis acidic species react with fluorobenzene and 1,2-difluorobenzene to yield [Cp*2M(κF-FC6H5) n ][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [Cp*2M(κ2 F-1,2-F2C6H4)][BPh4], the first examples of κF-fluorobenzene and κ2 F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)4]-, both Sc and Ti form [Cp*2M(κ2 F-C6F5)B(C6F5)3] contact ion pairs. The nature of the metal−fluoroarene interaction was studied by density functional theory (DFT) calculations and by comparison with the corresponding tetrahydrofuran (THF) adducts and was found to be predominantly electrostatic for all metals studied. |
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Bibliography: | ark:/67375/TPS-W9L5WX5R-8 istex:B8DC70CE8F237F44778A4D19AE69E46ABECEE13A ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/ja054544i |