Bis(permethylindenyl) complexes of thorium: Synthesis, structure, and reactivity

Tina M. Trnka; Jeffrey B. Bonanno; Brian M. Bridgewater; Gerard Parkin

doi:10.1021/om010233e

Bis(permethylindenyl) complexes of thorium: Synthesis, structure, and reactivity

Tina M. Trnka, Jeffrey B. Bonanno, Brian M. Bridgewater, Gerard Parkin

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

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Abstract

A variety of thorium complexes incorporating the bulky permethylindenyl ligand (Ind* = C₉Me₇) have been synthesized and characterized. Specifically, the dichloride Ind*₂ThCl₂ is obtained by reaction of ThCl₄ with Ind*Li, from which Ind*₂ThMe₂, Ind*₂Th(NMe₂)₂, Ind*₂Th(NC₄H₄)₂, and Ind*₂Th(η³-H₃BH)₂ may be obtained by metathesis with MeLi, LiNMe₂, LiNC₄H₄, and Ca(BH₄)₂, respectively. In contrast to simple metathesis, reaction of Ind*₂-ThCl₂ with KN(SiMe₃)₂ yields the metallacycle Ind*₂Th(η²-CH₂SiMe₂ NSiMe₃). X-ray diffraction studies on Ind*₂ThCl₂, Ind*₂ThCl(μ-Cl)₂Li(tmeda), Ind*₂ThMe₂, Ind*₂Th(NMe₂)₂, Ind*₂-Th(η²-CH₂SiMe₂ NSiMe₃), and Ind*₂Th(η³-H₃BH)₂ indicate that the permethylindenyl ligands in these complexes exhibit a variety of conformations.

Original language	English (US)
Pages (from-to)	3255-3264
Number of pages	10
Journal	Organometallics
Volume	20
Issue number	15
DOIs	https://doi.org/10.1021/om010233e
State	Published - Jul 23 2001
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Bis(permethylindenyl) complexes of thorium: Synthesis, structure, and reactivity",

abstract = "A variety of thorium complexes incorporating the bulky permethylindenyl ligand (Ind* = C9Me7) have been synthesized and characterized. Specifically, the dichloride Ind*2ThCl2 is obtained by reaction of ThCl4 with Ind*Li, from which Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2Th(NC4H4)2, and Ind*2Th(η3-H3BH)2 may be obtained by metathesis with MeLi, LiNMe2, LiNC4H4, and Ca(BH4)2, respectively. In contrast to simple metathesis, reaction of Ind*2-ThCl2 with KN(SiMe3)2 yields the metallacycle Ind*2Th(η2-CH2SiMe2 NSiMe3). X-ray diffraction studies on Ind*2ThCl2, Ind*2ThCl(μ-Cl)2Li(tmeda), Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2-Th(η2-CH2SiMe2 NSiMe3), and Ind*2Th(η3-H3BH)2 indicate that the permethylindenyl ligands in these complexes exhibit a variety of conformations.",

author = "Trnka, {Tina M.} and Bonanno, {Jeffrey B.} and Bridgewater, {Brian M.} and Gerard Parkin",

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AU - Trnka, Tina M.

AU - Bonanno, Jeffrey B.

AU - Bridgewater, Brian M.

AU - Parkin, Gerard

PY - 2001/7/23

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N2 - A variety of thorium complexes incorporating the bulky permethylindenyl ligand (Ind* = C9Me7) have been synthesized and characterized. Specifically, the dichloride Ind*2ThCl2 is obtained by reaction of ThCl4 with Ind*Li, from which Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2Th(NC4H4)2, and Ind*2Th(η3-H3BH)2 may be obtained by metathesis with MeLi, LiNMe2, LiNC4H4, and Ca(BH4)2, respectively. In contrast to simple metathesis, reaction of Ind*2-ThCl2 with KN(SiMe3)2 yields the metallacycle Ind*2Th(η2-CH2SiMe2 NSiMe3). X-ray diffraction studies on Ind*2ThCl2, Ind*2ThCl(μ-Cl)2Li(tmeda), Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2-Th(η2-CH2SiMe2 NSiMe3), and Ind*2Th(η3-H3BH)2 indicate that the permethylindenyl ligands in these complexes exhibit a variety of conformations.

AB - A variety of thorium complexes incorporating the bulky permethylindenyl ligand (Ind* = C9Me7) have been synthesized and characterized. Specifically, the dichloride Ind*2ThCl2 is obtained by reaction of ThCl4 with Ind*Li, from which Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2Th(NC4H4)2, and Ind*2Th(η3-H3BH)2 may be obtained by metathesis with MeLi, LiNMe2, LiNC4H4, and Ca(BH4)2, respectively. In contrast to simple metathesis, reaction of Ind*2-ThCl2 with KN(SiMe3)2 yields the metallacycle Ind*2Th(η2-CH2SiMe2 NSiMe3). X-ray diffraction studies on Ind*2ThCl2, Ind*2ThCl(μ-Cl)2Li(tmeda), Ind*2ThMe2, Ind*2Th(NMe2)2, Ind*2-Th(η2-CH2SiMe2 NSiMe3), and Ind*2Th(η3-H3BH)2 indicate that the permethylindenyl ligands in these complexes exhibit a variety of conformations.

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Bis(permethylindenyl) complexes of thorium: Synthesis, structure, and reactivity

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