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

Abstract

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(iii)-μ-H-Al(iii) moiety.

Aluminum Nanocubes Have Sharp Corners

“…This Al–C interaction appears to slightly buckle the square Tiμ 2 H 2 Al fragment in the bimetallic complex, pushing the hydrides together and predisposing the molecule to the reductive elimination of H 2 . Formation of Al–C bonds were previously observed through X-ray crystallography of an analogous bimetallic Ti–Al complex stabilized by a tris­(trimethyl silane) methyl (C­(TMS) 3 ) ligand, TiCp 2 μ 2 H 2 AlHC­(TMS) 3 . When heated to 100 °C in benzene, TiCp 2 μ 2 H 2 AlHC­(TMS) 3 loses H 2 and forms the dimer (TiCp­(C 5 H 4 )­μ 2 H 2 AlC­(TMS) 3 ) 2 , which contains two Al–C bonds created by C–H bond activation of the cyclopentadienyl rings …”

Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex

“…To gain insight into whether any actinide–aluminum bond was present in 4 and 5 , we explored spectroscopic and theoretical techniques that probed mixing between the Al 3p and actinide 6d/5f orbitals. Frozen solution EPR spectra for 4 and 5 as well as a reported titanium analogue, Cp 2 Ti( iii )(μ-H) 2 Al(H)C(SiMe 3 ) 3 ( 6 ), 63 are presented in Fig. 3 .…”

“… 61 , 62 Here we report the synthesis and characterization of Th–Al and U–Al heterobimetallics using an alanate ligand recently found to support a Ti–Al bimetallic. 63 Electron paramagnetic resonance (EPR) studies of the Th( iii ) complex demonstrated significant contributions from Al valence orbitals to the singly occupied molecular orbital (SOMO) compared with the Ti( iii ) analogue. A comprehensive DFT investigation confirmed a new metal–metal interaction paradigm that has not been observed previously for actinides, involving electron donation from the 6d-orbitals in the Th( iii )–Al complex and from the 5f orbitals in the U( iii )–Al complex.…”

A Volatile Dialane Complex from Ring Expansion of an N-Heterocyclic Carbene and Its Use in the Thermal Atomic Layer Deposition of Aluminum Metal Films

“…The molecular structure of 5 is a hydride-bridged heterobimetallic Ti–Al complex (Figure ). Several similar hydride-bridged Ti–Al complexes have been reported and the purple color appears to be characteristic. − The N–Al(1)–C bond angle increased from 90.49(10)° in 1 to 100.34(9) in 5 .…”