21793-61-3

Upstream product

• 74-94-2 dimethylamine borane 
• 917-54-4 methyllithium 

Downstream Products

• 74-94-2 dimethylamine borane 
• 23884-11-9 cyclic(dimethylamino borane) dimer 
• 1838-13-7 dimethylamine borane 
• 1192372-95-4 [Rh((borane)*(NMe₂BH₂)*(dimethylamine))(P(i-Bu)3)2][B(3,5-C₆H₃(CF₃)2)4] 
• 1073349-16-2 [Rh(H)2((borane)*(dimethylamine))(P(i-Bu)3)2][B(3,5-C₆H₃(CF₃)2)4] 
• 1192372-97-6 [Rh(H)2((borane)*(NMe₂BH₂)*(dimethylamine))(P(i-Bu)3)2][B(3,5-C₆H₃(CF₃)2)4] 
• 2386-98-3 bis(dimethylamino)borane 

Relevant academic research and scientific papers

Heterogeneous dehydrocoupling of amine-borane adducts by skeletal nickel catalysts

Skeletal Ni, produced by the selective leaching of Al from a Ni/Al alloy, has been successfully employed in the catalytic dehydrogenation of various amineborane adducts. The combination of low cost and facile single-step synthesis make this system a potentially attractive alternative to the previously described precious metal and other first-row metal catalysts. The heterogeneous nature of the catalyst facilitates convenient product purification, and this is the first such system to be based on a first-row transition metal. Catalytic dehydrocoupling of Me2NH·BH3 (1) and Et2NH3 BH3 (5) was demonstrated using 5 mol % skeletal Ni catalyst at 20 °C and produced [Me2N·BH2]2 (2) and [Et2N-BH2]2/Et2NdBH2 (6), respectively. The related adduct iPr2NH3 BH 3 (7) was also dehydrogenated to afford iPr2NdBH2 (8) but with significant catalyst deactivation. Catalytic dehydrocoupling of MeNH2 3 BH3 (9) was found to yield the cyclic triborazane [MeNH-BH 2]3 (10) as the major product, whereas high molecular weight poly- (methylaminoborane) [MeNH-BH2]n (11) (Mw = 78 000 Da, PDI = 1.52) was formed when stoichiometric quantities of Ni were used. Similar reactivity was also observed with NH3 3 BH3 (12), which produced cyclic oligomers and insoluble polymers, [NH2-BH2] xx (14), under catalytic and stoichiometric Ni loadings, respectively. Catalyst recycling was hindered by gradual poisoning. A study of possible catalyst poisons suggested that BH3 was the most likely surface poison, in line with previous work on colloidal Rh catalysts. Catalytic borane adducts using skeletal Cu and Fe was also explored. Skeletal Cu was found to be a less active dehydrogenation catalyst for amine-borane adducts but also yielded poly(methylaminoborane) under stoichiometric conditions on reaction with MeNH2 · BH3 (9). Skeletal Fe was found to be completely inactive towardamine-borane dehydrogenationr

Mechanistic insights into dehydrocoupling of amine boranes using dinuclear zirconocene complexes

Catalytic dehydrocoupling of H3B·NMe2H using the in situ system Cp2Zr(Cl)(μ-Me3SiC3SiMe3)Zr(Cl)Cp2 (1)/MeLi was studied as a model for previously reported dehydropolymerisation of H3B·NMeH2. NMR and UV-vis spectroscopic monitoring of the precatalyst activation sequence as well as a series of stoichiometric experiments showed that formation of a zirconocene dimethyl complex (2) is not relevant for activation of the precatalyst. Instead, deprotonation of H3B·NMe2H and reaction of thus formed Li[NMe2BH3] is proposed to result in the formation of Zr amidoborane and hydride species. DFT analysis using such complexes as active species showed a pathway for formation of H2 and H2BNMe2. 1H NMR spectroscopic monitoring and stoichiometric control experiments revealed the formation of unusual diamagnetic dinuclear complexes Cp2Zr(C2SiMe3)(μ-R)ZrCp2 (R = CH2SiMe3, 7; R = H, 9) formed by activation of the allenediide unit of the precatalyst 1. Such species can be regarded as rare single-component catalysts for the dehydrocoupling of amine boranes. This journal is

Dehydropolymerisation of Methylamine Borane and an N-Substituted Primary Amine Borane Using a PNP Fe Catalyst

Dehydropolymerisation of methylamine borane (H3B?NMeH2) using the well-known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH2CH2PiPr2)2) (1) gives poly(aminoborane)s by a chain-growth mechanism. In toluene, rapid dehydrogenation of H3B?NMeH2 following first-order behaviour as a limiting case of a more general underlying Michaelis–Menten kinetics is observed, forming aminoborane H2B=NMeH, which selectively couples to give high-molecular-weight poly(aminoborane)s (H2BNMeH)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 (H3B?NMe2H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H3B?N(CH2SiMe3)H2 was studied in homo- and co-dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s.

Catalytic Dehydrocoupling of Amine-Boranes using Cationic Zirconium(IV)-Phosphine Frustrated Lewis Pairs

A series of novel, intramolecular Zr(IV)/P frustrated Lewis pairs (FLPs) based on cationic zirconocene fragments with a variety of ancillary cyclopentadienyl and 2-phosphinoaryloxide (-O(C6H4)PR2, R = tBu and 3,5-CF3-(C6H3)) ligands are reported and their activity as catalysts for the dehydrocoupling of dimethylamine-borane (Me2NH·BH3) assessed. The FLP system [(C9H7)2ZrO(C6H4)PtBu2][B(C6F5)4] is shown to give unprecedented turnover frequencies (TOF) for a catalyst based on a group 4 metal (TOF ≥ 600 h-1), while also proving to be the most efficient FLP catalyst reported to date. The mechanism of this reaction has been probed using analogous intermolecular Zr(IV)/P FLPs, permitting deconvolution of the reactions taking place at both the Lewis acidic and basic sites. Elucidation of this mechanism revealed an interesting cooperative two-cycle process where one cycle is FLP mediated and the other, a redistribution of a linear diborazane intermediate, relies solely on the presence of a Zr(IV) Lewis acid.

Catalytic dehydrogenation of dimethylamine borane by group 4 metallocene alkyne complexes and homoleptic amido compounds

Dehydrogenation of Me2NH·BH3 (1) by group 4 metallocene alkyne complexes of the type Cp2M(L)(η2- Me3SiC2SiMe3) [Cp = η5- cyclopentadienyl; M = Ti, no L (2Ti); M = Zr, L = pyridine (2Zr)] and group 4 metal amido complexes of the type M(NMe2)4 [M = Ti (8Ti), Zr (8Zr)] is presented.

Ruthenium-catalyzed dimethylamineborane dehydrogenation: Stepwise metal-centered dehydrocyclization

Amine-borane dehydrogenation: Ruthenium PNP amido pincer complex I catalyzes the dehydrocoupling of dimethylamineborane to cyclic dimer (Me 2NBH2)2. The results are in agreement with a mechanism including initial alternati