Method for the production of hydrogen from the dehydrocoupling of amine boranes

摘要

The present disclosure relates to processes and methods of generating hydrogen via the dehydrocoupling of amine boranes using ligand-stabilized homogenous metal catalysts. The amine-borane is shown by the formula (I), R1R2N—BHR3R4. A process is also shown for the preparation of a linear, branched or cyclic polymer which comprises a repeating unit of the formula (II), —[R1R2N—BR3R4]-n, by reacting HR1R2N—BHR3R4 in the presence of at least one ligand-stabilized metal catalyst.

主权项

1. A method for the production of hydrogen comprising
(a) dehydrocoupling at least one amine-borane of the formula (I)
R1R2N—BHR3R4  (I) wherein R1, R2, R3 and R4 are each simultaneously or independently selected from H, fluoro-substituted-C1-20alkyl, optionally substituted C1-20alkyl and optionally substituted C6-14aryl or any two of R1, R2, R3 and R4 are linked to form an optionally substituted C2-10alkylene, which together with the nitrogen and/or boron atoms to which they are attached, forms a ring, wherein the optional substituents are independently selected from one or more of C1-6alkyl, halo, halo-substituted C1-6alkyl, C3-10cycloalkyl, aryl and heteroaryl, in the presence of at least one ligand-stabilized metal catalyst in an inert solvent and, optionally, in the presence of a base, wherein the metal catalyst comprises at least one ligand that bonds to the metal through a nitrogen; and (b) optionally collecting hydrogen produced in the dehydrocoupling of the at least one amine borane, wherein the at least one ligand that bonds to the metal through a nitrogen is selected from one or more of an N2, PN, PNP, PNNP, NPN, NS and NNN ligand wherein N2 is a bidentate ligand of the formula R5R6N-Q1-NR7R8; PN is a bindante ligand of the formula R9R10P-Q2-NR11R12; PNP is a tridentate ligand of the formula R13R14P-Q3-NR15-Q4-PR16R17; PNNP is a tetradentate ligand of the formula R18R19P-Q5-NR20-Q6-NR21-Q7-PR22R23; NPN is a tridentate ligand of the formula R24R25N-Q8-PR26-Q9-NR27R28; NS is a bidentate ligand of the formula R29R30N-Q10-SR31; and NNN is a tridentate ligand of the formula R32R33N-Q11-NR34-Q12-NR35R36, wherein R5-R36 are independently selected from unsubstituted or substituted C1-10alkyl, unsubstituted or substituted C2-10alkenyl, unsubstituted or substituted C3-10cycloalkyl, unsubstituted or substituted C6-14aryl, or any two adjacent or geminal R5-R36 groups are bonded together to form, together with the atoms to which they are attached, a 5-14-membered monocyclic, polycyclic, heterocyclic, carbocyclic, saturated or unsaturated ring system and any of R5-R36, including rings formed therewith are achiral or chiral; and Q1-Q12 are independently selected from unsubstituted or substituted C1-C10alkylene and unsubstituted or substituted C1-C10alkenylene where adjacent or geminal substituents on Q1-Q12 are joined together to form, including the atoms to which they are attached, one or more unsubstituted or substituted 5-14-membered monocyclic, polycyclic, heterocyclic, carbocyclic, saturated, unsaturated or metallocenyl ring systems, and/or one or more of the carbon atoms in Q1-Q12 is optionally replaced with a heteromoiety selected from O, S, NH and N(C1-6alkyl) and any of Q1-Q12 is chiral or achiral, and wherein the optional substituents are independently selected from one or more of C1-6alkyl, halo, halo-substituted C1-6alkyl, C3-10cycloalkyl, aryl and heteroaryl.