Dehydropolymerisation of methylamine borane using a dinuclear 1,3-allenediyl bridged zirconocene complex.

The dinuclear zirconocene chloride complex 1 is a highly active precatalyst for the dehydropolymerisation of methylamine borane. Comparison with mononuclear Zr chlorides and related dinuclear complexes suggests that the nature of the bridging motif is essential for the unique reactivity of 1.

Synthesis of Rh(iii) thiophosphinito pincer hydrido complexes by base-free C-H bond activation at room temperature.

Rhodium(iii) thiophosphinito pincer hydrido complexes were synthesised by C-H activation under exceptionally mild conditions at room temperature without additional base or irradiation and fully characterised by multinuclear NMR spectroscopy and X-ray crystallography. C-H activation under these mild conditions contrasts with the reactivity of related systems with POCOP ligands.

Formation of high-molecular weight polyaminoborane by Fe hydride catalysed dehydrocoupling of methylamine borane.

The complex [(PNHP)Fe(H)(CO)(HBH3)] (PNHP = HN(CH2CH2Pi-Pr2)2) serves as a catalyst precursor for the selective dehydrocoupling of methylamine borane at room temperature, tentatively via an off-metal polymerisation pathway.

Iridium(iii) hydrido complexes for the catalytic dehydrogenation of hydrazine borane.

The synthesis of 3,5-disubstituted cyclometalated iridium(iii) hydrido complexes of the type [3,5-R2(POCOP)IrHX] (3,5-R2(POCOP) = κ3-C5HR2-2,6-(OPtBu2)2 with R = t-Bu, COOMe; X = Cl, H) is described. All complexes were investigated in the catalytic dehydrogenation of hydrazine borane and compared with the unsubstituted compounds [(POCOP)IrHX] (X = Cl, H). All catalysts are highly active and recyclable, clearly maintaining hydrogen production activity. The dehydrogenation products were structurally characterised by solid state NMR and FTIR spectroscopy. Experimental observations were complemented by a dispersion-corrected DFT study to rationalise the mechanism of hydrazine borane dehydrogenation.