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In this case, treatment of the resulting \u03ba<jats:sup>1<\/jats:sup>\u2010formate complex with triethylsilane does not lead to regeneration of the hydride precursor. However, when combined with B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>, (<jats:sup>Dipp<\/jats:sup>L)Ga(Ad)H catalyses the reductive hydrosilylation of CO<jats:sub>2<\/jats:sub>. Under stoichiometric conditions, the addition of one equivalent of B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> to (<jats:sup>Dipp<\/jats:sup>L)Ga(Ad)H leads to the formation of a 3\u2010coordinate cationic gallane complex, partnered with a hydroborate anion, [(<jats:sup>Dipp<\/jats:sup>L)Ga(Ad)][HB(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>]. This complex rapidly hydrometallates carbon dioxide and catalyses the selective reduction of CO<jats:sub>2<\/jats:sub> to the formaldehyde oxidation level at 60\u2009\u00b0C in the presence of Et<jats:sub>3<\/jats:sub>SiH (yielding H<jats:sub>2<\/jats:sub>C(OSiEt<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>). When catalysis is undertaken in the presence of excess B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>, appreciable enhancement of activity is observed, with a corresponding reduction in selectivity: the product distribution includes H<jats:sub>2<\/jats:sub>C(OSiEt<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>, CH<jats:sub>4<\/jats:sub> and O(SiEt<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>. While this system represents proof\u2010of\u2010concept in CO<jats:sub>2<\/jats:sub> hydrosilylation by a gallium hydride system, the TOF values obtained are relatively modest (max. 10\u2005h<jats:sup>\u22121<\/jats:sup>). This is attributed to the strength of binding of the formatoborate anion to the gallium centre in the catalytic intermediate (<jats:sup>Dipp<\/jats:sup>L)Ga(Ad){OC(H)OB(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>}, and the correspondingly slow rate of the turnover\u2010limiting hydrosilylation step. In turn, this strength of binding can be related to the relatively high Lewis acidity measured for the [(<jats:sup>Dipp<\/jats:sup>L)Ga(Ad)]<jats:sup>+<\/jats:sup> cation (AN=69.8).<\/jats:p>","DOI":"10.1002\/chem.202004408","type":"journal-article","created":{"date-parts":[[2020,11,10]],"date-time":"2020-11-10T16:48:46Z","timestamp":1605026926000},"page":"2138-2148","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Partnering a Three\u2010Coordinate Gallium Cation with a Hydroborate Counter\u2010Ion for the Catalytic Hydrosilylation of CO<sub>2<\/sub>"],"prefix":"10.1002","volume":"27","author":[{"given":"Alexa","family":"Caise","sequence":"first","affiliation":[{"name":"Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford  South Parks Road Oxford OX1 3QR 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