2012
DOI: 10.1002/anie.201207903
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Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes

Abstract: Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates.

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Cited by 84 publications
(100 citation statements)
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“…Solvent effects have also been noted by Manners and Weller in the off-metal dimerisation of H 2 B¼NMe 2 , with the rate of dimerisation being accelerated in MeCN [19,20]. [69,92], Re [86], Cr [98] and Rh [65]. Systems remaining in a constant oxidation state, however, include cationic Rh [66] and Ir [19,70], as well as bifunctional Ru catalysts [21,59] Manners and co-workers have suggested closely related, but alternative, schemes for the processes occurring in the dehydrogenation and dehydrocoupling of ammonia-borane and primary and secondary amine-boranes, as shown in Scheme 49 [5,123].…”
Section: Late Transition Metalsmentioning
confidence: 84%
“…Solvent effects have also been noted by Manners and Weller in the off-metal dimerisation of H 2 B¼NMe 2 , with the rate of dimerisation being accelerated in MeCN [19,20]. [69,92], Re [86], Cr [98] and Rh [65]. Systems remaining in a constant oxidation state, however, include cationic Rh [66] and Ir [19,70], as well as bifunctional Ru catalysts [21,59] Manners and co-workers have suggested closely related, but alternative, schemes for the processes occurring in the dehydrogenation and dehydrocoupling of ammonia-borane and primary and secondary amine-boranes, as shown in Scheme 49 [5,123].…”
Section: Late Transition Metalsmentioning
confidence: 84%
“…[1, 17, 53, 54] For example, addition of D 2 to [Ir(PCy 3 ) 2 (H) 2 (η 2 η 2 –H 3 BNMeH 2 )][BAr F 4 ] results in H/D exchange only at Ir–H and B–H. [33] However, products that arise from formal N–H activation over B–H activation have been isolated [55, 56] or postulated [57, 58] for neutral systems and are also proposed as intermediates in amine–borane dehydropolymerization. [20, 59] It thus appears likely that the cyclic nature of the amine–borane in 5 results in more levelled B–H/N–H activation energies.…”
Section: Resultsmentioning
confidence: 99%
“…25 The close agreement between the calculated strength of the agostic bond and the experimental efficiency of the dehydrogenation processes may suggest that the agostic intermediate might have a prominent role in the reaction mechanism.…”
mentioning
confidence: 71%