Chemoselectivity diversity in the reaction of LiNC6F 5SiMe3 with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes

Sinai Aharonovich; Mark Botoshansky; Robert M. Waymouth; Moris S. Eisen

doi:10.1021/ic100696r

Chemoselectivity diversity in the reaction of LiNC₆F ₅SiMe₃ with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes

Sinai Aharonovich, Mark Botoshansky, Robert M. Waymouth, Moris S. Eisen

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

18 Scopus citations

Abstract

Unlike the reaction of LiNTMS₂· TMEDA (TMS = SiMe ₃; TMEDA = tetramethylethylenediamine) with 2-cyanopyridine, which results in the nearly exclusive formation of the amidinate, (Me ₃SiNC₆F₅)Li · TMEDA (1) reacts with 2-cyanopyridine in toluene to yield quantitatively the lithium pyridyltetrafluorobenzimidazolate complex [C₆F₄N ₂C(2-C₅H₄N)]Li · TMEDA (3). In this work, the reactivity of complex 1 toward aromatic nitriles Ar-CN (Ar = Ph, o-OMeC₆H₄, C₆F₅, 2-pyridyl) was examined. Whereas complex 1 fails to react with o-methoxybenzonitrile, its reaction with benzonitrile or pentafluorobenzonitrile gives triphenyl-1,3,5- triazine (4) or the hexacoordinate lithium polymer [LiN(4-NCC₆F ₄)(C₆F₅) · THF · TMEDA] _n (7), respectively. When 1 is reacted with 2-cyanopyridine in tetrahydrofuran (THF), the benzimidazolate coordination polymer {[C ₆F₄N₂C(2-C₅H₄N)]Li · THF}_n (5) is obtained. Herein we discuss how this diverse chemoselectivity in the reaction of the examined lithium N-silylated amides LiNRTMS · TMEDA (R = TMS, C₆F₅) with nitriles is influenced by the electronic properties of the nitrile or amide substituents and by the ability of these substituents to interact with the lithium or silicon atoms. Further, we present the syntheses and structures of zirconium tris(pyridyltetrafluorobenzimidazolate) chloride (10) and zirconium bis(dimethylamido)(pyridyltetrafluorobenzimidazolate) chloride · THF (11) complexes. These complexes, the first prepared zirconium mono-and tris(benzimidazolate)s, were crystallographically characterized and examined in the polymerization of propylene with methyl aluminoxane (1:1000 Zr/Al molar ratio).

Original language	English
Pages (from-to)	9217-9229
Number of pages	13
Journal	Inorganic Chemistry
Volume	49
Issue number	20
DOIs	https://doi.org/10.1021/ic100696r
State	Published - 18 Oct 2010
Externally published	Yes

Access to Document

10.1021/ic100696r

Cite this

@article{4289cbfb7f2044e1a7ba5ccbd6b4ada1,

title = "Chemoselectivity diversity in the reaction of LiNC6F 5SiMe3 with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes",

abstract = "Unlike the reaction of LiNTMS2· TMEDA (TMS = SiMe 3; TMEDA = tetramethylethylenediamine) with 2-cyanopyridine, which results in the nearly exclusive formation of the amidinate, (Me 3SiNC6F5)Li · TMEDA (1) reacts with 2-cyanopyridine in toluene to yield quantitatively the lithium pyridyltetrafluorobenzimidazolate complex [C6F4N 2C(2-C5H4N)]Li · TMEDA (3). In this work, the reactivity of complex 1 toward aromatic nitriles Ar-CN (Ar = Ph, o-OMeC6H4, C6F5, 2-pyridyl) was examined. Whereas complex 1 fails to react with o-methoxybenzonitrile, its reaction with benzonitrile or pentafluorobenzonitrile gives triphenyl-1,3,5- triazine (4) or the hexacoordinate lithium polymer [LiN(4-NCC6F 4)(C6F5) · THF · TMEDA] n (7), respectively. When 1 is reacted with 2-cyanopyridine in tetrahydrofuran (THF), the benzimidazolate coordination polymer {[C 6F4N2C(2-C5H4N)]Li · THF}n (5) is obtained. Herein we discuss how this diverse chemoselectivity in the reaction of the examined lithium N-silylated amides LiNRTMS · TMEDA (R = TMS, C6F5) with nitriles is influenced by the electronic properties of the nitrile or amide substituents and by the ability of these substituents to interact with the lithium or silicon atoms. Further, we present the syntheses and structures of zirconium tris(pyridyltetrafluorobenzimidazolate) chloride (10) and zirconium bis(dimethylamido)(pyridyltetrafluorobenzimidazolate) chloride · THF (11) complexes. These complexes, the first prepared zirconium mono-and tris(benzimidazolate)s, were crystallographically characterized and examined in the polymerization of propylene with methyl aluminoxane (1:1000 Zr/Al molar ratio).",

author = "Sinai Aharonovich and Mark Botoshansky and Waymouth, {Robert M.} and Eisen, {Moris S.}",

year = "2010",

month = oct,

day = "18",

doi = "10.1021/ic100696r",

language = "英语",

volume = "49",

pages = "9217--9229",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

Chemoselectivity diversity in the reaction of LiNC₆F ₅SiMe₃ with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes. / Aharonovich, Sinai; Botoshansky, Mark; Waymouth, Robert M. et al.
In: Inorganic Chemistry, Vol. 49, No. 20, 18.10.2010, p. 9217-9229.

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

TY - JOUR

T1 - Chemoselectivity diversity in the reaction of LiNC6F 5SiMe3 with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes

AU - Aharonovich, Sinai

AU - Botoshansky, Mark

AU - Waymouth, Robert M.

AU - Eisen, Moris S.

PY - 2010/10/18

Y1 - 2010/10/18

N2 - Unlike the reaction of LiNTMS2· TMEDA (TMS = SiMe 3; TMEDA = tetramethylethylenediamine) with 2-cyanopyridine, which results in the nearly exclusive formation of the amidinate, (Me 3SiNC6F5)Li · TMEDA (1) reacts with 2-cyanopyridine in toluene to yield quantitatively the lithium pyridyltetrafluorobenzimidazolate complex [C6F4N 2C(2-C5H4N)]Li · TMEDA (3). In this work, the reactivity of complex 1 toward aromatic nitriles Ar-CN (Ar = Ph, o-OMeC6H4, C6F5, 2-pyridyl) was examined. Whereas complex 1 fails to react with o-methoxybenzonitrile, its reaction with benzonitrile or pentafluorobenzonitrile gives triphenyl-1,3,5- triazine (4) or the hexacoordinate lithium polymer [LiN(4-NCC6F 4)(C6F5) · THF · TMEDA] n (7), respectively. When 1 is reacted with 2-cyanopyridine in tetrahydrofuran (THF), the benzimidazolate coordination polymer {[C 6F4N2C(2-C5H4N)]Li · THF}n (5) is obtained. Herein we discuss how this diverse chemoselectivity in the reaction of the examined lithium N-silylated amides LiNRTMS · TMEDA (R = TMS, C6F5) with nitriles is influenced by the electronic properties of the nitrile or amide substituents and by the ability of these substituents to interact with the lithium or silicon atoms. Further, we present the syntheses and structures of zirconium tris(pyridyltetrafluorobenzimidazolate) chloride (10) and zirconium bis(dimethylamido)(pyridyltetrafluorobenzimidazolate) chloride · THF (11) complexes. These complexes, the first prepared zirconium mono-and tris(benzimidazolate)s, were crystallographically characterized and examined in the polymerization of propylene with methyl aluminoxane (1:1000 Zr/Al molar ratio).

AB - Unlike the reaction of LiNTMS2· TMEDA (TMS = SiMe 3; TMEDA = tetramethylethylenediamine) with 2-cyanopyridine, which results in the nearly exclusive formation of the amidinate, (Me 3SiNC6F5)Li · TMEDA (1) reacts with 2-cyanopyridine in toluene to yield quantitatively the lithium pyridyltetrafluorobenzimidazolate complex [C6F4N 2C(2-C5H4N)]Li · TMEDA (3). In this work, the reactivity of complex 1 toward aromatic nitriles Ar-CN (Ar = Ph, o-OMeC6H4, C6F5, 2-pyridyl) was examined. Whereas complex 1 fails to react with o-methoxybenzonitrile, its reaction with benzonitrile or pentafluorobenzonitrile gives triphenyl-1,3,5- triazine (4) or the hexacoordinate lithium polymer [LiN(4-NCC6F 4)(C6F5) · THF · TMEDA] n (7), respectively. When 1 is reacted with 2-cyanopyridine in tetrahydrofuran (THF), the benzimidazolate coordination polymer {[C 6F4N2C(2-C5H4N)]Li · THF}n (5) is obtained. Herein we discuss how this diverse chemoselectivity in the reaction of the examined lithium N-silylated amides LiNRTMS · TMEDA (R = TMS, C6F5) with nitriles is influenced by the electronic properties of the nitrile or amide substituents and by the ability of these substituents to interact with the lithium or silicon atoms. Further, we present the syntheses and structures of zirconium tris(pyridyltetrafluorobenzimidazolate) chloride (10) and zirconium bis(dimethylamido)(pyridyltetrafluorobenzimidazolate) chloride · THF (11) complexes. These complexes, the first prepared zirconium mono-and tris(benzimidazolate)s, were crystallographically characterized and examined in the polymerization of propylene with methyl aluminoxane (1:1000 Zr/Al molar ratio).

UR - http://www.scopus.com/inward/record.url?scp=78549285342&partnerID=8YFLogxK

U2 - 10.1021/ic100696r

DO - 10.1021/ic100696r

M3 - 文章

C2 - 20857913

AN - SCOPUS:78549285342

SN - 0020-1669

VL - 49

SP - 9217

EP - 9229

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Chemoselectivity diversity in the reaction of LiNC₆F ₅SiMe₃ with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this