期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 51, 页码 13624-13635出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201802603
关键词
aluminium; carbon dioxide; diketiminates; hydride; reduction
资金
- EPSRC
- Oxford-SCG Centre of Excellence
- EU Marie Curie program [PIEF-GA-2013-626441]
A series of beta-diketiminate stabilized aluminium hydrides of the type (Nacnac)Al(R)H has been synthesized offering variation in the auxiliary R substituent and in the Nacnac backbone. These show significant variation in the nature of the Al-H bond: electron-donating R groups give rise to weaker (and presumably more hydridic) Al-H bonds, leading to enhanced rates of reactivity towards CO2. The resulting kappa(1)-formate complexes (Nacnac)Al(R){OC(O)H} have been isolated and their reactivity towards B-H-containing reductants probed. In the case of HBpin no reaction is observed (even under forcing conditions), while the more reactive boranes HBcat and {H(9-BBN)}(2) ultimately yield boryloxy complexes of the type (Nacnac)Al(R)(OBX2) (X-2=cat, 9-BBN). However, no hint of Al-O/B-H metathesis is observed even under forcing conditions. With BH3 center dot SMe2 the major product is a related boryloxy system, although (uniquely) in this case a minor product is observed which contains an Al-H bond. We hypothesize that (Nacnac)Al(R)(kappa(2)-BH4) is formed (despite the unfavourable thermodynamics of Al-O/B-H metathesis) due to the additional driving force provided by coordination of the strongly Lewis acidic BH3 unit to the Al-H bond. That said, we find that (unlike the analogous gallium systems) no catalytic turnover can be achieved in the reduction of CO2 by boranes mediated by these aluminium hydrides.
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