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Issue 32, 2014
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DFT examination of rare α-SiMe3 abstraction in Ta(NMe2)4[N(SiMe3)2]: formation of the imide compound Ta(<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>NSiMe3)(NMe2)3 and its trapping to give guanidinate imides

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Abstract

A density functional theory (DFT) investigation on the formation of Ta([double bond, length as m-dash]NSiMe3)(NMe2)3 (B) and Me3SiNMe2 (C) from Ta(NMe2)4[N(SiMe3)2] is reported. Three different ground-state minima are computed for Ta(NMe2)4[N(SiMe3)2], and of these only the stereoisomer based on a square pyramid (A2) with an apical N(SiMe3)2 group undergoes α-elimination to give Ta([double bond, length as m-dash]NSiMe3)(NMe2)3 (B) and Me3SiNMe2 (C). The barrier computed for the concerted α-elimination is in agreement with the results from our earlier experimental study. The thermodynamics for the monomer–dimer equilibrium involving Ta([double bond, length as m-dash]NSiMe3)(NMe2)3 (B) has been computationally evaluated, and the preference for the dimeric form of the compound is discussed relative to the Nugent imide derivative Ta([double bond, length as m-dash]NCMe3)(NMe2)3, which exists as a monomer. The trapping of the intermediate B by the heterocumulene MeN[double bond, length as m-dash]C[double bond, length as m-dash]NMe has been modeled, and the mechanism involved in the formation of the guanidinate-based insertion products Ta(NSiMe3)(NMe2)2[MeNC(NMe2)NMe] (G1) and Ta(NSiMe3)(NMe2)[MeNC(NMe2)NMe]2 (I) is presented.

Graphical abstract: DFT examination of rare α-SiMe3 abstraction in Ta(NMe2)4[N(SiMe3)2]: formation of the imide compound Ta(<img border='0' src='http://www.rsc.org/images/entities/char_e001.gif' alt='[double bond, length as m-dash]'/>NSiMe3)(NMe2)3 and its trapping to give guanidinate imides

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Publication details

The article was received on 23 May 2014, accepted on 20 Jun 2014 and first published on 20 Jun 2014


Article type: Paper
DOI: 10.1039/C4DT01521E
Citation: Dalton Trans., 2014,43, 12390-12395
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    DFT examination of rare α-SiMe3 abstraction in Ta(NMe2)4[N(SiMe3)2]: formation of the imide compound Ta(<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>NSiMe3)(NMe2)3 and its trapping to give guanidinate imides

    M. G. Richmond and Z. Xue, Dalton Trans., 2014, 43, 12390
    DOI: 10.1039/C4DT01521E

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