No abstract

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

Dehydropolymerisation of methylamine borane (H 3 B⋅NMeH 2 ) using the well‐known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH 2 CH 2 P i Pr 2 ) 2 ) ( 1 ) gives poly(aminoborane)s by a chain‐growth mechanism. In toluene, rapid dehydrogenation of H 3 B⋅NMeH 2 following first‐order behaviour as a limiting case of a more general underlying Michaelis–Menten kinetics is observed, forming aminoborane H 2 B=NMeH, which selectively couples to give high‐molecular‐weight poly(aminoborane)s (H 2 BNMeH) n and only traces of borazine (HBNMe) 3 by depolymerisation after full conversion. Based on a series of comparative experiments using structurally related Fe catalysts and dimethylamine borane (H 3 B⋅NMe 2 H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H 3 B⋅N(CH 2 SiMe 3 )H 2 was studied in homo‐ and co‐dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s.

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.

The bis(thiophosphinite) pincer complexes [(RPSCSPR)Rh(py)(H)(Cl)] (RPSCSPR = C6H4-2,6-(SPR2)2 with R = iPr, 2a and R = Ph, 2a) are prepared by metalation of the ligand precursor with [Rh(cod)Cl]2 in the...