{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T02:01:39Z","timestamp":1791079299297,"version":"4.1.0"},"reference-count":76,"publisher":"Wiley","issue":"21","license":[{"start":{"date-parts":[[2019,9,30]],"date-time":"2019-09-30T00:00:00Z","timestamp":1569801600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","award":["637394"],"award-info":[{"award-number":["637394"]}],"id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemCatChem"],"published-print":{"date-parts":[[2019,11,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The previously reported dimeric NHI aluminum dihydrides <jats:bold>1\u2009a<\/jats:bold>,<jats:bold>b<\/jats:bold>, as well as the bis(NHI) aluminum dihydride salt <jats:bold>9<\/jats:bold><jats:sup>+<\/jats:sup>[OTs]<jats:sup>\u2212<\/jats:sup>, the bis(NHI) boron dihydride salt <jats:bold>10<\/jats:bold><jats:sup>+<\/jats:sup>[OTs]<jats:sup>\u2212<\/jats:sup>, and the \u201cfree\u201d bis(NHI) ligand <jats:bold>12<\/jats:bold> were investigated with regard to their activity as a homogenous (pre)catalyst in the hydroboration (i.\u2009e. catalytic reduction) of carbon dioxide (CO<jats:sub>2<\/jats:sub>) in chloroform under mild conditions (i.\u2009e. room temperature, 1\u2005atm; NHI=N\u2010heterocyclic imine, Ts=tosyl). Borane dimethylsulfide complex and catecholborane were used as a hydride source. Surprisingly, the less sterically hindered <jats:bold>1\u2009a<\/jats:bold> exhibited lower catalytic activity than the bulkier <jats:bold>1\u2009b<\/jats:bold>. A similarly unexpected discrepancy was found with the lower catalytic activity of <jats:bold>10<\/jats:bold><jats:sup>+<\/jats:sup> in comparison to the one of the bis(NHI) <jats:bold>12<\/jats:bold>. The latter is incorporated as the ligand to the boron center in <jats:bold>10<\/jats:bold><jats:sup>+<\/jats:sup>. To elucidate possible mechanisms for CO<jats:sub>2<\/jats:sub> reduction the compounds were subjected to stoichiometric reactivity studies with the borane or CO<jats:sub>2<\/jats:sub>. Aluminum carboxylates <jats:bold>4<\/jats:bold>, <jats:bold>6<\/jats:bold>, and <jats:bold>7<\/jats:bold><jats:sup>+<\/jats:sup> with two, four, and one formate group per two aluminum centers were isolated. Also, the boron formate salt <jats:bold>11<\/jats:bold><jats:sup>+<\/jats:sup>[OTs]<jats:sup>\u2212<\/jats:sup> was characterized. Selected metal formates were subjected to stoichiometric reactions with boranes and\/or tested as a catalyst. We conclude that each type of catalyst (<jats:bold>1\u2009a<\/jats:bold>,<jats:bold>b<\/jats:bold>, <jats:bold>9<\/jats:bold><jats:sup>+<\/jats:sup>, <jats:bold>10<\/jats:bold><jats:sup>+<\/jats:sup>, <jats:bold>12<\/jats:bold>) follows an individual mechanistic pathway for CO<jats:sub>2<\/jats:sub> reduction.<\/jats:p>","DOI":"10.1002\/cctc.201901255","type":"journal-article","created":{"date-parts":[[2019,9,17]],"date-time":"2019-09-17T12:53:51Z","timestamp":1568724831000},"page":"5275-5281","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":54,"title":["Catalytic CO<sub>2<\/sub> Reduction with Boron\u2010 and Aluminum Hydrides"],"prefix":"10.1002","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4173-7231","authenticated-orcid":false,"given":"Daniel","family":"Franz","sequence":"first","affiliation":[{"name":"Department of Chemistry Catalysis Research Center and Institute of Silicon Chemistry Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstr. 4 Garching bei M\u00fcnchen 85748 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Jandl","sequence":"additional","affiliation":[{"name":"Department of Chemistry Catalysis Research Center and Institute of Silicon Chemistry Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstr. 4 Garching bei M\u00fcnchen 85748 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Claire","family":"Stark","sequence":"additional","affiliation":[{"name":"Department of Chemistry Catalysis Research Center and Institute of Silicon Chemistry Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstr. 4 Garching bei M\u00fcnchen 85748 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6685-6352","authenticated-orcid":false,"given":"Shigeyoshi","family":"Inoue","sequence":"additional","affiliation":[{"name":"Department of Chemistry Catalysis Research Center and Institute of Silicon Chemistry Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstr. 4 Garching bei M\u00fcnchen 85748 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