Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

Rainer Zitz; Johann Hlina; Henning Arp; Dominik Kinschel; Christoph Marschner; Judith Baumgartner

doi:10.1021/acs.inorgchem.9b00866

Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

Rainer Zitz, Johann Hlina, Henning Arp, Dominik Kinschel, Christoph Marschner, Judith Baumgartner

Institut für Anorganische Chemie (6330)

Publikation: Beitrag in einer Fachzeitschrift › Artikel › Begutachtung

Abstract

A number of paramagnetic silylated d ¹ group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp ₂ MCl ₂ ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp ₂ Hf{Si(SiMe ₃ ) ₃ } ₂ ] ^- was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe ₃ ) ₂ ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp ₂ Zr{Si(SiMe ₃ ) ₃ } ₂ ] ^- could be obtained by reduction of Cp ₂ Zr{Si(SiMe ₃ ) ₃ } ₂ with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp ₃ Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp ₃ Ln Si(SiMe ₃ ) ₃ ] ^- with either [18-crown-6·K] ⁺ or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d ¹ or f ⁿ electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

Originalsprache	englisch
Seiten (von - bis)	7107-7117
Seitenumfang	11
Fachzeitschrift	Inorganic Chemistry
Jahrgang	58
Ausgabenummer	10
DOIs	https://doi.org/10.1021/acs.inorgchem.9b00866
Publikationsstatus	Veröffentlicht - Mai 2019

ASJC Scopus subject areas

Anorganische Chemie
Physikalische und Theoretische Chemie

Zugriff auf Dokument

10.1021/acs.inorgchem.9b00866

Andere Dateien und Links

http://www.scopus.com/inward/record.url?scp=85066020859&partnerID=8YFLogxK

Dieses zitieren

@article{e69da4ce532a42e4819343d66a381d14,

title = "Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands",

abstract = "A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis. ",

author = "Rainer Zitz and Johann Hlina and Henning Arp and Dominik Kinschel and Christoph Marschner and Judith Baumgartner",

year = "2019",

month = may,

doi = "10.1021/acs.inorgchem.9b00866",

language = "English",

volume = "58",

pages = "7107--7117",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

AU - Zitz, Rainer

AU - Hlina, Johann

AU - Arp, Henning

AU - Kinschel, Dominik

AU - Marschner, Christoph

AU - Baumgartner, Judith

PY - 2019/5

Y1 - 2019/5

N2 - A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

AB - A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

UR - http://www.scopus.com/inward/record.url?scp=85066020859&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.9b00866

DO - 10.1021/acs.inorgchem.9b00866

M3 - Article

SN - 0020-1669

VL - 58

SP - 7107

EP - 7117

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -

Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

Abstract

ASJC Scopus subject areas

Zugriff auf Dokument

Andere Dateien und Links

Fingerprint

Dieses zitieren