Hydride oxidation from a titanium-aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

Chemical Science
Alexandra C BrownJohn Arnold

Abstract

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(iii)-μ-H-Al(iii) moiety. Combining different stoichiometries amounts of Cp2TiCl and KH3AlC(TMS)3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp2Ti(μ-H)2(H)AlC(TMS)3 (2) or trimetallic (Cp2Ti)2(μ-H)3(H)AlC(TMS)3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The nature of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C-H activation from the Ti(iii) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(iv) promotes bimolecular reductive elimination of dihydrogen to form a Ti(iii) product.

References

Sep 13, 2007·Chemical Reviews·Shin-Ichi OrimoCraig M Jensen
May 15, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Beatriz CorderoSantiago Alvarez
Jun 27, 2009·Chemical Communications : Chem Comm·Ragaiy ZidanAndrew G Harter
Nov 8, 2012·Angewandte Chemie·Shuhui YowMark R Crimmin
Feb 6, 2013·Chemical Communications : Chem Comm·Chelladurai GanesamoorthyRoland A Fischer
Jul 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Johannes ThomasTorsten Beweries
Jun 4, 2014·Journal of the American Chemical Society·Terry ChuGeorgii I Nikonov
Nov 5, 2016·Angewandte Chemie·Alison C McQuilkenTimothy H Warren
Jan 11, 2017·Chemical Communications : Chem Comm·Michael J Butler, Mark R Crimmin
Oct 1, 2015·Chemical Science·Olga EkkertMark R Crimmin

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Citations

Aug 20, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A BoreenJohn Arnold
May 22, 2018·Chemical Science·Alison B AltmanJohn Arnold
Jan 8, 2019·Journal of the American Chemical Society·Benjamin D ClarkNaomi J Halas
Aug 10, 2019·ACS Nano·Benjamin D ClarkNaomi J Halas
Aug 28, 2021·Chemical Reviews·Matthew M D RoyEric Rivard
Nov 5, 2021·Chemistry : a European Journal·Estefanía Del HornoCarlos Yélamos

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Methods Mentioned

BETA
NMR
X-ray

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