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This work reports on the first catalyst\u2010free CO<jats:sub>2<\/jats:sub> hydroboration with a neutral boron compound, the nucleophilic diborane [HB(hpp)]<jats:sub>2<\/jats:sub>, <jats:bold>1<\/jats:bold> (hpp=1,3,4,6,7,8\u2010hexahydro\u20102<jats:italic>H<\/jats:italic>\u2010pyrimido[1,2\u2010a]pyrimidinate). Further hydroboration reactions to bis(boryl)acetals are possible. In acetonitrile, but not in dichloromethane solutions, hydroboration of a first CO<jats:sub>2<\/jats:sub> is followed by hydroboration of a second CO<jats:sub>2<\/jats:sub> molecule. Detailed kinetic measurements for both hydroboration steps were carried out and the influence of the solvent and the addition of a Lewis base on the rate constants analyzed. In contrast to catalyst\u2010free hydroboration of CO<jats:sub>2<\/jats:sub>, hydroboration of the less electrophilic acetone requires the presence of an activating Lewis acid.<\/jats:p>","DOI":"10.1002\/chem.201804612","type":"journal-article","created":{"date-parts":[[2018,9,11]],"date-time":"2018-09-11T09:41:15Z","timestamp":1536658875000},"page":"16983-16986","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Catalyst\u2010Free Hydroboration of CO<sub>2<\/sub> With a Nucleophilic Diborane(4)"],"prefix":"10.1002","volume":"24","author":[{"given":"Markus","family":"Frick","sequence":"first","affiliation":[{"name":"Anorganisch-Chemisches Institut Ruprecht-Karls-University Heidelberg  Im Neuenheimer Feld\u2005270 69120 Heidelberg"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julian","family":"Horn","sequence":"additional","affiliation":[{"name":"Anorganisch-Chemisches Institut Ruprecht-Karls-University Heidelberg  Im Neuenheimer Feld\u2005270 69120 Heidelberg"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hubert","family":"Wadepohl","sequence":"additional","affiliation":[{"name":"Anorganisch-Chemisches Institut Ruprecht-Karls-University Heidelberg  Im Neuenheimer Feld\u2005270 69120 Heidelberg"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elisabeth","family":"Kaifer","sequence":"additional","affiliation":[{"name":"Anorganisch-Chemisches Institut Ruprecht-Karls-University Heidelberg  Im Neuenheimer Feld\u2005270 69120 Heidelberg"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8111-3047","authenticated-orcid":false,"given":"Hans\u2010J\u00f6rg","family":"Himmel","sequence":"additional","affiliation":[{"name":"Anorganisch-Chemisches Institut Ruprecht-Karls-University Heidelberg  Im Neuenheimer Feld\u2005270 69120 Heidelberg"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,11,2]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01602a063"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.19586180105"},{"key":"e_1_2_2_4_1","unstructured":"\u00a0"},{"key":"e_1_2_2_5_2","first-page":"486","volume":"83","author":"Brown H. 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