Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes

MW Bouwkamp; PHM Budzelaar; J Gercama; ID Morales; J de Wolf; A Meetsma; SI Troyanov; JH Teuben; B Hessen; Peter H.M. Budzelaar; Isabel Del Hierro Morales; Sergei I. Troyanov

doi:10.1021/ja054544i

Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes

MW Bouwkamp, PHM Budzelaar, J Gercama, ID Morales, J de Wolf, A Meetsma, SI Troyanov, JH Teuben, B Hessen^*, Peter H.M. Budzelaar, Isabel Del Hierro Morales, Sergei I. Troyanov

^*Corresponding author for this work

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Abstract

The ionic metallocene complexes [Cp*M-2][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*M-2(kF-FC6H5)(n)][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [CP*M-2(k(2)F-1,2-F2C6H4)][BPh4], the first examples of kF-fluorobenzene and k(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)(4)](-), both Sc and Ti form [CP*M-2(k(2) 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.

Original language	English
Pages (from-to)	14310-14319
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	127
Issue number	41
DOIs	https://doi.org/10.1021/ja054544i
Publication status	Published - 19-Oct-2005

Keywords

OLEFIN POLYMERIZATION CATALYSTS
BETA-AGOSTIC INTERACTIONS
C-H BONDS
MOLECULAR-STRUCTURE
CRYSTAL-STRUCTURES
COORDINATION CHEMISTRY
METALLOCENE CATALYSTS
MULTIPLE SYNTHESES
BASIS-SETS
REACTIVITY

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CCDC 291079: Experimental Crystal Structure Determination
Bouwkamp, M. (Contributor), Budzelaar, P. H. M. (Contributor), Gercama, J. (Contributor), Hierro Morales ,del, M. (Contributor), Wolf ,de, J. (Contributor), Troyanov, S. I. (Contributor), Meetsma, A. (Contributor), Teuben, J. (Contributor) & Hessen, B. (Contributor), University of Groningen, 29-Nov-2005
DOI: 10.5517/cc9rwnk
Dataset
CCDC 291077: Experimental Crystal Structure Determination
Bouwkamp, M. (Contributor), Budzelaar, P. H. M. (Contributor), Gercama, J. (Contributor), Hierro Morales ,del, M. (Contributor), Wolf ,de, J. (Contributor), Meetsma, A. (Contributor), Troyanov, S. I. (Contributor), Teuben, J. (Contributor) & Hessen, B. (Contributor), University of Groningen, 29-Nov-2005
DOI: 10.5517/cc9rwlh
Dataset
CCDC 291073: Experimental Crystal Structure Determination
Bouwkamp, M. (Contributor), Budzelaar, P. H. M. (Contributor), Gercama, J. (Contributor), Hierro Morales ,del, M. (Contributor), Wolf ,de, J. (Contributor), Meetsma, A. (Contributor), Troyanov, S. I. (Contributor), Teuben, J. (Contributor) & Hessen, B. (Contributor), University of Groningen, 29-Nov-2005
DOI: 10.5517/cc9rwgc
Dataset

Cite this

Bouwkamp, MW., Budzelaar, PHM., Gercama, J., Morales, ID., de Wolf, J., Meetsma, A., Troyanov, SI., Teuben, JH., Hessen, B., Budzelaar, P. H. M., Hierro Morales, I. D., & Troyanov, S. I. (2005). Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes. Journal of the American Chemical Society, 127(41), 14310-14319. https://doi.org/10.1021/ja054544i

@article{9ae78aa350de4cac84e481cdbc12ccc2,

title = "Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes",

abstract = "The ionic metallocene complexes [Cp*M-2][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*M-2(kF-FC6H5)(n)][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [CP*M-2(k(2)F-1,2-F2C6H4)][BPh4], the first examples of kF-fluorobenzene and k(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)(4)](-), both Sc and Ti form [CP*M-2(k(2) 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.",

keywords = "OLEFIN POLYMERIZATION CATALYSTS, BETA-AGOSTIC INTERACTIONS, C-H BONDS, MOLECULAR-STRUCTURE, CRYSTAL-STRUCTURES, COORDINATION CHEMISTRY, METALLOCENE CATALYSTS, MULTIPLE SYNTHESES, BASIS-SETS, REACTIVITY",

author = "MW Bouwkamp and PHM Budzelaar and J Gercama and ID Morales and {de Wolf}, J and A Meetsma and SI Troyanov and JH Teuben and B Hessen and Budzelaar, {Peter H.M.} and {Hierro Morales}, {Isabel Del} and Troyanov, {Sergei I.}",

year = "2005",

month = oct,

day = "19",

doi = "10.1021/ja054544i",

language = "English",

volume = "127",

pages = "14310--14319",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "AMER CHEMICAL SOC",

number = "41",

}

TY - JOUR

T1 - Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes

AU - Bouwkamp, MW

AU - Budzelaar, PHM

AU - Gercama, J

AU - Morales, ID

AU - de Wolf, J

AU - Meetsma, A

AU - Troyanov, SI

AU - Teuben, JH

AU - Hessen, B

AU - Budzelaar, Peter H.M.

AU - Hierro Morales, Isabel Del

AU - Troyanov, Sergei I.

PY - 2005/10/19

Y1 - 2005/10/19

N2 - The ionic metallocene complexes [Cp*M-2][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*M-2(kF-FC6H5)(n)][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [CP*M-2(k(2)F-1,2-F2C6H4)][BPh4], the first examples of kF-fluorobenzene and k(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)(4)](-), both Sc and Ti form [CP*M-2(k(2) 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.

AB - The ionic metallocene complexes [Cp*M-2][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*M-2(kF-FC6H5)(n)][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [CP*M-2(k(2)F-1,2-F2C6H4)][BPh4], the first examples of kF-fluorobenzene and k(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)(4)](-), both Sc and Ti form [CP*M-2(k(2) 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.

KW - OLEFIN POLYMERIZATION CATALYSTS

KW - BETA-AGOSTIC INTERACTIONS

KW - C-H BONDS

KW - MOLECULAR-STRUCTURE

KW - CRYSTAL-STRUCTURES

KW - COORDINATION CHEMISTRY

KW - METALLOCENE CATALYSTS

KW - MULTIPLE SYNTHESES

KW - BASIS-SETS

KW - REACTIVITY

U2 - 10.1021/ja054544i

DO - 10.1021/ja054544i

M3 - Article

SN - 0002-7863

VL - 127

SP - 14310

EP - 14319

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 41

ER -

Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes

Abstract

Keywords

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Datasets

CCDC 291079: Experimental Crystal Structure Determination

CCDC 291077: Experimental Crystal Structure Determination

CCDC 291073: Experimental Crystal Structure Determination

Cite this