A General, Rhodium‐Catalyzed, Synthesis of Deuterated Boranes and N‐Methyl Polyaminoboranes. Issue 21 (23rd March 2018)

• Record Type: Journal Article
• Authors: Colebatch, Annie L.; Hawkey Gilder, Benjamin W.; Whittell, George R.; Oldroyd, Nicola L.; Manners, Ian; Weller, Andrew S.
• Is Part Of: Chemistry. Volume 24:Issue 21(2018)
• Page Start: 5450
• Page End: 5455
• Publication Date: 2018-03-23
• Subjects: borane -- dehydropolymerization -- deuterium -- H/D exchange -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201800737
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η 6 ‐FC6 H5 )][BAr F 4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3, H3 B⋅SMe2 and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N ‐methylamine‐borane: R3 B⋅NMeR2 1‐ d x (R=H, D; x= 0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of1‐ d x to give deuterated polyaminoboranes. Mechanistic studies suggest a metal‐based polymerization involving an unusual hybrid coordination insertion chain‐growth/step‐growth mechanism. Abstract : Deuterated amine‐boranes, prepared in high isotopic purities and yields, can be dehydropolymerized to give deuterated polyaminoboranes; for which mechanistic studies suggest an unusual hybrid coordination insertion chain‐growth/step‐growth mechanism.