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The synthesis and characterization of Me<jats:sub>3<\/jats:sub>PC(H)B(<jats:italic>i<\/jats:italic>Bu)<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>), consisting of small Me substituents on phosphorous and <jats:italic>i<\/jats:italic>Bu residues on boron, is reported. Compound <jats:bold>1<\/jats:bold> is accessible through a novel synthetic approach, which has been further elucidated through DFT studies. The reactivity of <jats:bold>1<\/jats:bold> towards various small molecules was probed and compared with that of a previously published derivative, Ph<jats:sub>3<\/jats:sub>PC(Me)BEt<jats:sub>2<\/jats:sub> (<jats:bold>2<\/jats:bold>). Both \u03b1\u2010BCPs react with NH<jats:sub>3<\/jats:sub> to undergo heterolytic N\u2212H bond cleavage. Different di\u2010 and trimeric ring structures were observed in the reaction products of <jats:bold>1<\/jats:bold> with CO and CO<jats:sub>2<\/jats:sub>. With PhNCO and PHNCS, the expected insertion products [Me<jats:sub>3<\/jats:sub>PC(H)(PhNCO)B(<jats:italic>i<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>] and [Me<jats:sub>3<\/jats:sub>PC(H)(PhNCS)B(<jats:italic>i<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>], respectively, were isolated.<\/jats:p>","DOI":"10.1002\/chem.201902681","type":"journal-article","created":{"date-parts":[[2019,7,29]],"date-time":"2019-07-29T08:02:32Z","timestamp":1564387352000},"page":"12206-12213","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Reactivity of a Sterically Unencumbered \u03b1\u2010Borylated Phosphorus Ylide towards Small Molecules"],"prefix":"10.1002","volume":"25","author":[{"given":"Michael","family":"Radius","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry Division Molecular Chemistry Karlsruhe Institute of Technology (KIT)  Engesserstr. 15 76131 Karlsruhe 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