The exchange reactions between trialkylboranes and BH₃^.THF and BH₃^.DMS are discussed. The reactions afford alkylboron hydrides in complexed monomeric compounds or as dimers. An important collection of NMR data was done from these experiments. Between them the exchange reactions of 9-borabicyclononane (9-BBN) were analyzed. The hydroboration reaction steps of isoprene was followed by NMR and some important reactions intermediates were discovered as is the case of 3-methylboracyclopentane. The syntheses of monocyclic and bicyclic boron compounds N→B coordinated is discussed. The heterocycles were formed using 9-BBN, phenylboronic and diphenylborinic esters of aminoalcohols, aminophenols and aminoacids. The synthesis of optically active compounds in which the boron and nitrogen atoms are stereogenic centers of stable configuration is described. Some N→B bond energy and ¹¹B data is provided.