Molybdenum catalyzed ammonia borane dehydrogenation: oxidation state specific mechanisms.

Molybdenum catalyzed ammonia borane dehydrogenation: oxidation state specific mechanisms.
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DOI:
10.1021/ja5059923
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发表时间:
2014-08-13
影响因子:
15
通讯作者:
Agapie, Theodor
Agapie, Theodor
中科院分区:
化学1区
文献类型:
--
作者:
Buss, Joshua A.;Edouard, Guy A.;Cheng, Christine;Shi, Jade;Agapie, Theodor

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虽然已知了许多用于氨硼烷(AB)脱氢的催化剂,但释放出当量为2的氢气的催化剂并不常见。在这里,我们报道了一个具有金属-芳烃相互作用的对三苯基二膦配体1支撑的钼配合物的合成。Mo0N_2络合物5和MoII双(乙腈)络合物4都表现出高水平的AB脱氢,释放超过2.0当量的H2。反应速率、脱氢程度和反应机理随催化剂前氧化状态的不同而不同。对几种与AB化学有关的钼氢化物(MoII(H)2、[MoII(H)]+和[MoIV(H)3]+)进行了表征。
Though numerous catalysts for the dehydrogenation of ammonia borane (AB) are known, those that release >2 equiv of H2 are uncommon. Herein, we report the synthesis of Mo complexes supported by a para-terphenyl diphosphine ligand, 1, displaying metal–arene interactions. Both a Mo0 N2 complex, 5, and a MoII bis(acetonitrile) complex, 4, exhibit high levels of AB dehydrogenation, releasing over 2.0 equiv of H2. The reaction rate, extent of dehydrogenation, and reaction mechanism vary as a function of the precatalyst oxidation state. Several Mo hydrides (MoII(H)2, [MoII(H)]+, and [MoIV(H)3]+) relevant to AB chemistry were characterized.
DOI: 10.1021/om960360o
发表时间: 1997-03-18
期刊: ORGANOMETALLICS
影响因子: 2.8
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通讯作者: Hall, MB
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