Extremely Bulky Amido and Amidinato Complexes of Boron and Aluminium Halides: Synthesis and Reduction Studies

Edwin W.Y. Wong; Deepak Dange; Lea Fohlmeister; Terrance J. Hadlington; Cameron Jones

doi:10.1071/CH13175

RESEARCH ARTICLE

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Extremely Bulky Amido and Amidinato Complexes of Boron and Aluminium Halides: Synthesis and Reduction Studies

Edwin W.Y. Wong ^A , Deepak Dange ^A , Lea Fohlmeister ^A , Terrance J. Hadlington ^A and Cameron Jones ^A ^B

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, PO Box 23, Monash University, Melbourne, Vic. 3800, Australia.

^B Corresponding author. Email: cameron.jones@monash.edu

Australian Journal of Chemistry 66(10) 1144-1154 https://doi.org/10.1071/CH13175
Submitted: 13 April 2013 Accepted: 7 May 2013 Published: 5 June 2013

Abstract

An extremely bulky secondary amine, HN(Ar^†)(SiPr₃ⁱ) HL^† (Ar^† = C₆H₂{C(H)Ph₂}₂Prⁱ−2,6,4) has been synthesised and deprotonated with KH in toluene, to afford the potassium amide [KL^†(η⁶-toluene)], which was structurally authenticated. Reaction of this with BBr₃ and AlBr₃, reproducibly gave the crystallographically characterised amido bromo-borane, [L^†B(H)Br], and aluminacycle, [AlBr₂{κ²-C,N-N(H)(SiPr₃ⁱ){C₆H₂[CPh₂][C(H)Ph₂]Prⁱ-2,6,4}}], respectively, via ligand C–H activation processes. The known secondary amines, HN(Dip)(Mes) (HL^Mes) and HN(Dip)(Trip) (HL^Trip) (Dip =2,6-diisopropylphenyl, Mes = mesityl, Trip = 2,4,6-triisopropylphenyl), have been structurally characterised, and deprotonated to give the in situ generated lithium amides, [Li(L^Mes)] and [Li(L^Trip)]. Reaction of these with BBr₃ and AlBr₃ has given the amido group 13 element halide complexes, [L^MesBBr₂] and [LAlBr₂(THF)] (L = L^Mes or L^Trip), the crystal structures of all of which have been determined. Synthetic routes to two new bulky amidine pro-ligands, ArN = C(Bu^t)-N(H)Ar, Ar = C₆H₂{C(H)Ph₂}₂Me-2,6,4 (Piso*H) or C₆H₂Pr₂ⁱ(CPh₃)-2,6,4 (Piso″H), have been developed, and the compounds crystallographically characterised. Deprotonation of Piso″H gave the potassium amidinate, [K(Piso″)], which was reacted with BBr₃ to give [(Piso″)BBr₂]. Reaction of Piso″H with AlMe₃ afforded [(Piso″)AlMe₂], which, when treated with I₂ yielded [(Piso″)AlI₂], the crystal structure of which was determined. Reductions of all of the prepared amido and amidinato group 13 element(iii) halide complexes were attempted using a variety of reducing reagents, with a view to prepare boron(i) or aluminium(i) complexes. While these were not successful, this study does offer synthetic inorganic chemists a variety of new very bulky anionic N-donor ligands, and boron/aluminium halide complexes thereof, for use in their own research.

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Extremely Bulky Amido and Amidinato Complexes of Boron and Aluminium Halides: Synthesis and Reduction Studies

Abstract

References

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