Conversion of (η5-C2B9H10R)TaX3 (X = Me, NMe2) to (η6-C2B9H10R)TaX′ (X′ = NMe2, azaallyl) in the absence of a reducing agent: synthesis and structure of tantallacarboranes incorporating an arachno-η6-C2B94− ligand

Li Xiang; Zuowei Xie

doi:10.1039/C4CC03981E

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Conversion of (η⁵-C₂B₉H₁₀R)TaX₃ (X = Me, NMe₂) to (η⁶-C₂B₉H₁₀R)TaX′ (X′ = NMe₂, azaallyl) in the absence of a reducing agent: synthesis and structure of tantallacarboranes incorporating an arachno-η⁶-C₂B₉⁴⁻ ligand†

Li Xiang^a and Zuowei Xie*^a

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* Corresponding authors

^a Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China
E-mail: zxie@cuhk.edu.hk
Fax: +852 26035057

Abstract

Heating a benzene solution of [η⁵-(Me₂NCH₂CH₂)C₂B₉H₁₀] Ta(NMe₂)₃ (1) in the presence of pyridine gave an unprecedented complex [η¹:η⁶-(Me₂NCH₂CH₂)C₂B₉H₁₀]Ta (NMe₂)(NC₅H₅) (2). On the other hand, reaction of (η⁵-C₂B₉H₁₁)TaMe₃ with adamantly isonitrile (AdNC) in dimethoxyethane (DME) at room temperature afforded another unexpected complex (η⁶-C₂B₉H₁₁)Ta[η³-C,C,N-CH₂C(CH₃)NAd](DME) (4). These results show that pyridine and DME are essential for the formation of 2 and 4, respectively. It is suggested that the nido-η⁵-C₂B₉H₁₀R²⁻ ligand in tantallacarboranes takes up two electrons released by reductive elimination to form an arachno-η⁶-C₂B₉H₁₀R⁴⁻ fragment via the cage C–C bond cleavage.

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Article information

DOI: https://doi.org/10.1039/C4CC03981E
Article type: Communication
Submitted: 24 May 2014
Accepted: 08 Jun 2014
First published: 09 Jun 2014

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Chem. Commun., 2014,50, 8249-8252

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Conversion of (η⁵-C₂B₉H₁₀R)TaX₃ (X = Me, NMe₂) to (η⁶-C₂B₉H₁₀R)TaX′ (X′ = NMe₂, azaallyl) in the absence of a reducing agent: synthesis and structure of tantallacarboranes incorporating an arachno-η⁶-C₂B₉⁴⁻ ligand

L. Xiang and Z. Xie, Chem. Commun., 2014, 50, 8249 DOI: 10.1039/C4CC03981E

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