Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions

Xinmin Yang; Wayne A. King; Michal Sabat; Tobin J Marks

Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions

Xinmin Yang, Wayne A. King, Michal Sabat, Tobin J Marks

Northwestern University

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

43 Citations (Scopus)

Abstract

Metal bis(dicarbollides) of the type M(B₉-C₂H₁₁)₂^- (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp′₂ThR]⁺X^- (Cp′ = η⁵-(CH₃)₅C₅; R = alkyl, H) as potential weakly coordinating unions. The reaction of Cp′₂Th(CH₃)₂ with [HNEt₃]⁺-[Co(B₉C₂H ₁₁)₂]^- and [HNEt₃]⁺[Fe(B₉C₂H₁₁) ₂]^- in hydrocarbon solvents affords [Cp′₂ThCH₃]⁺[Co(B₉C ₂H₁₁)²]^- (1) and [Cp′₂ThCH₃]₂²⁺[Fe(B ₉C₂H₁₁)₂]^2- (2), respectively. The structure of 2 reveals tight ion-pairing with three close Th⋯H-B bridging interactions (2.42(3), 2.50(3), 2.67-(4) Å). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp′₂Th[CH₂Si(CH₃)₃] ₂ with [HNEt₃]⁺-[Co(B₉C₂H ₁₁)₂]^- affords [Cp′₂ThCH₂Si(CH₃)₃] ⁺-[Co(B₉C₂H₁₁)₂] ^- (3), which slowly undergoes hydrogenolysis to yield [C′₂ThH]⁺[Co(B₉C₂H ₁₁)₂]^- (4).

Original language	English
Pages (from-to)	4254-4258
Number of pages	5
Journal	Organometallics
Volume	12
Issue number	10
Publication status	Published - 1993

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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title = "Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions",

abstract = "Metal bis(dicarbollides) of the type M(B9-C2H11)2- (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp′2ThR]+X- (Cp′ = η5-(CH3)5C5; R = alkyl, H) as potential weakly coordinating unions. The reaction of Cp′2Th(CH3)2 with [HNEt3]+-[Co(B9C2H 11)2]- and [HNEt3]+[Fe(B9C2H11) 2]- in hydrocarbon solvents affords [Cp′2ThCH3]+[Co(B9C 2H11)2]- (1) and [Cp′2ThCH3]22+[Fe(B 9C2H11)2]2- (2), respectively. The structure of 2 reveals tight ion-pairing with three close Th⋯H-B bridging interactions (2.42(3), 2.50(3), 2.67-(4) {\AA}). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp′2Th[CH2Si(CH3)3] 2 with [HNEt3]+-[Co(B9C2H 11)2]- affords [Cp′2ThCH2Si(CH3)3] +-[Co(B9C2H11)2] - (3), which slowly undergoes hydrogenolysis to yield [C′2ThH]+[Co(B9C2H 11)2]- (4).",

author = "Xinmin Yang and King, {Wayne A.} and Michal Sabat and Marks, {Tobin J}",

year = "1993",

language = "English",

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journal = "Organometallics",

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TY - JOUR

T1 - Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions

AU - Yang, Xinmin

AU - King, Wayne A.

AU - Sabat, Michal

AU - Marks, Tobin J

PY - 1993

Y1 - 1993

N2 - Metal bis(dicarbollides) of the type M(B9-C2H11)2- (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp′2ThR]+X- (Cp′ = η5-(CH3)5C5; R = alkyl, H) as potential weakly coordinating unions. The reaction of Cp′2Th(CH3)2 with [HNEt3]+-[Co(B9C2H 11)2]- and [HNEt3]+[Fe(B9C2H11) 2]- in hydrocarbon solvents affords [Cp′2ThCH3]+[Co(B9C 2H11)2]- (1) and [Cp′2ThCH3]22+[Fe(B 9C2H11)2]2- (2), respectively. The structure of 2 reveals tight ion-pairing with three close Th⋯H-B bridging interactions (2.42(3), 2.50(3), 2.67-(4) Å). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp′2Th[CH2Si(CH3)3] 2 with [HNEt3]+-[Co(B9C2H 11)2]- affords [Cp′2ThCH2Si(CH3)3] +-[Co(B9C2H11)2] - (3), which slowly undergoes hydrogenolysis to yield [C′2ThH]+[Co(B9C2H 11)2]- (4).

AB - Metal bis(dicarbollides) of the type M(B9-C2H11)2- (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp′2ThR]+X- (Cp′ = η5-(CH3)5C5; R = alkyl, H) as potential weakly coordinating unions. The reaction of Cp′2Th(CH3)2 with [HNEt3]+-[Co(B9C2H 11)2]- and [HNEt3]+[Fe(B9C2H11) 2]- in hydrocarbon solvents affords [Cp′2ThCH3]+[Co(B9C 2H11)2]- (1) and [Cp′2ThCH3]22+[Fe(B 9C2H11)2]2- (2), respectively. The structure of 2 reveals tight ion-pairing with three close Th⋯H-B bridging interactions (2.42(3), 2.50(3), 2.67-(4) Å). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp′2Th[CH2Si(CH3)3] 2 with [HNEt3]+-[Co(B9C2H 11)2]- affords [Cp′2ThCH2Si(CH3)3] +-[Co(B9C2H11)2] - (3), which slowly undergoes hydrogenolysis to yield [C′2ThH]+[Co(B9C2H 11)2]- (4).

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Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions

Abstract

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