Low-valent pentafulvene titanium dinitrogen complex as a precursor for cationic titanium complexes

Axel Scherer; Detlev Haase; Wolfgang Saak; Ruediger Beckhaus; Auke Meetsma; Marco W. Bouwkamp; Rüdiger Beckhaus

doi:10.1021/om900875e

Low-valent pentafulvene titanium dinitrogen complex as a precursor for cationic titanium complexes

Axel Scherer, Detlev Haase, Wolfgang Saak, Ruediger Beckhaus^*, Auke Meetsma, Marco W. Bouwkamp, Rüdiger Beckhaus

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

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Abstract

Treatment of titanium dinitrogen complex [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti](2)(mu-N(2)) (1) with ferrocenium borate, [Cp(2)Fe][BPh(4)], in THF results in oxidation of the titanium center, affording the titanium(IV) pentafulvene compound [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti(THF)][BPh(4)] (2). Treatment of I with anilinium reagent [PhNMe(2)H][BPh(4)] results ill the formation of cationic titanocene(III) complexes. In THF, the titanocene cation is stabilized by two THF solvent molecules, whereas the tetraphenylborate anion is bound to the metal center when the reaction is performed in toluene its it solvent, Treatment of 1 with B(C(6)F(5))(3) affords zwitterionic [Cp*{eta(5)-C(5)H(3)(C(11)H(14))(B{C(6)F(5)}(3)}Ti(THF)] (7). Results show the versatility of pentafulvene complex 1 in the preparation of cationic titanium complexes.

Original language	English
Pages (from-to)	6969-6974
Number of pages	6
Journal	Organometallics
Volume	28
Issue number	24
DOIs	https://doi.org/10.1021/om900875e
Publication status	Published - 28-Dec-2009

Keywords

OLEFIN POLYMERIZATION
CRYSTAL-STRUCTURE
ORGANOMETALLIC CHEMISTRY
METALLOCENE COMPLEXES
CATALYSTS
TITANOCENE
TRIS(PENTAFLUOROPHENYL)BORANE
TETRAPHENYLBORATE
DERIVATIVES
REACTIVITY

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10.1021/om900875e

2009OrganometallicsSchererSupp.pdfFinal publisher's version, 307 KB
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CCDC 906462: Experimental Crystal Structure Determination
Scherer, A. (Contributor), Haase, D. (Contributor), Saak, W. (Contributor), Beckhaus, R. (Contributor), Meetsma, A. (Contributor) & Bouwkamp, M. (Contributor), University of Groningen, 18-Oct-2012
DOI: 10.5517/cczf7qb
Dataset
CCDC 906461: Experimental Crystal Structure Determination
Scherer, A. (Contributor), Haase, D. (Contributor), Saak, W. (Contributor), Beckhaus, R. (Contributor), Meetsma, A. (Contributor) & Bouwkamp, M. (Contributor), University of Groningen, 18-Oct-2012
DOI: 10.5517/cczf7p9
Dataset
CCDC 906463: Experimental Crystal Structure Determination
Scherer, A. (Contributor), Haase, D. (Contributor), Saak, W. (Contributor), Beckhaus, R. (Contributor), Meetsma, A. (Contributor) & Bouwkamp, M. (Contributor), University of Groningen, 18-Oct-2012
DOI: 10.5517/cczf7rc
Dataset

Cite this

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title = "Low-valent pentafulvene titanium dinitrogen complex as a precursor for cationic titanium complexes",

abstract = "Treatment of titanium dinitrogen complex [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti](2)(mu-N(2)) (1) with ferrocenium borate, [Cp(2)Fe][BPh(4)], in THF results in oxidation of the titanium center, affording the titanium(IV) pentafulvene compound [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti(THF)][BPh(4)] (2). Treatment of I with anilinium reagent [PhNMe(2)H][BPh(4)] results ill the formation of cationic titanocene(III) complexes. In THF, the titanocene cation is stabilized by two THF solvent molecules, whereas the tetraphenylborate anion is bound to the metal center when the reaction is performed in toluene its it solvent, Treatment of 1 with B(C(6)F(5))(3) affords zwitterionic [Cp*{eta(5)-C(5)H(3)(C(11)H(14))(B{C(6)F(5)}(3)}Ti(THF)] (7). Results show the versatility of pentafulvene complex 1 in the preparation of cationic titanium complexes.",

keywords = "OLEFIN POLYMERIZATION, CRYSTAL-STRUCTURE, ORGANOMETALLIC CHEMISTRY, METALLOCENE COMPLEXES, CATALYSTS, TITANOCENE, TRIS(PENTAFLUOROPHENYL)BORANE, TETRAPHENYLBORATE, DERIVATIVES, REACTIVITY",

author = "Axel Scherer and Detlev Haase and Wolfgang Saak and Ruediger Beckhaus and Auke Meetsma and Bouwkamp, {Marco W.} and R{\"u}diger Beckhaus",

year = "2009",

month = dec,

day = "28",

doi = "10.1021/om900875e",

language = "English",

volume = "28",

pages = "6969--6974",

journal = "Organometallics",

issn = "0276-7333",

publisher = "AMER CHEMICAL SOC INC",

number = "24",

}

TY - JOUR

T1 - Low-valent pentafulvene titanium dinitrogen complex as a precursor for cationic titanium complexes

AU - Scherer, Axel

AU - Haase, Detlev

AU - Saak, Wolfgang

AU - Beckhaus, Ruediger

AU - Meetsma, Auke

AU - Bouwkamp, Marco W.

AU - Beckhaus, Rüdiger

PY - 2009/12/28

Y1 - 2009/12/28

N2 - Treatment of titanium dinitrogen complex [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti](2)(mu-N(2)) (1) with ferrocenium borate, [Cp(2)Fe][BPh(4)], in THF results in oxidation of the titanium center, affording the titanium(IV) pentafulvene compound [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti(THF)][BPh(4)] (2). Treatment of I with anilinium reagent [PhNMe(2)H][BPh(4)] results ill the formation of cationic titanocene(III) complexes. In THF, the titanocene cation is stabilized by two THF solvent molecules, whereas the tetraphenylborate anion is bound to the metal center when the reaction is performed in toluene its it solvent, Treatment of 1 with B(C(6)F(5))(3) affords zwitterionic [Cp*{eta(5)-C(5)H(3)(C(11)H(14))(B{C(6)F(5)}(3)}Ti(THF)] (7). Results show the versatility of pentafulvene complex 1 in the preparation of cationic titanium complexes.

AB - Treatment of titanium dinitrogen complex [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti](2)(mu-N(2)) (1) with ferrocenium borate, [Cp(2)Fe][BPh(4)], in THF results in oxidation of the titanium center, affording the titanium(IV) pentafulvene compound [Cp*(eta(6)-C(5)H(4)=C(10)H(14))Ti(THF)][BPh(4)] (2). Treatment of I with anilinium reagent [PhNMe(2)H][BPh(4)] results ill the formation of cationic titanocene(III) complexes. In THF, the titanocene cation is stabilized by two THF solvent molecules, whereas the tetraphenylborate anion is bound to the metal center when the reaction is performed in toluene its it solvent, Treatment of 1 with B(C(6)F(5))(3) affords zwitterionic [Cp*{eta(5)-C(5)H(3)(C(11)H(14))(B{C(6)F(5)}(3)}Ti(THF)] (7). Results show the versatility of pentafulvene complex 1 in the preparation of cationic titanium complexes.

KW - OLEFIN POLYMERIZATION

KW - CRYSTAL-STRUCTURE

KW - ORGANOMETALLIC CHEMISTRY

KW - METALLOCENE COMPLEXES

KW - CATALYSTS

KW - TITANOCENE

KW - TRIS(PENTAFLUOROPHENYL)BORANE

KW - TETRAPHENYLBORATE

KW - DERIVATIVES

KW - REACTIVITY

U2 - 10.1021/om900875e

DO - 10.1021/om900875e

M3 - Article

VL - 28

SP - 6969

EP - 6974

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 24

ER -

Low-valent pentafulvene titanium dinitrogen complex as a precursor for cationic titanium complexes

Abstract

Keywords

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Datasets

CCDC 906462: Experimental Crystal Structure Determination

CCDC 906461: Experimental Crystal Structure Determination

CCDC 906463: Experimental Crystal Structure Determination

Cite this