Small Chains of Main Group Elements by BH 3 Adduct Formation of t Bu 2 E‐N(H)‐E t Bu 2 (E = P, As)

Borane adducts of bis (di‐ tert ‐butylphosphanyl)amine ( 1a ) and bis (di‐ tert ‐butylarsino)amine ( 1b ) are reported. Based on quantum‐chemical investigations in combination with experimental results, it is demonstrated that the tautomerism known for t Bu 2 P‐N(H)‐P t Bu 2 ( 1a ), can be observed for the mono adduct t Bu 2 P‐N(H)‐P(BH 3 ) t Bu 2 ( 2a ) as well, whereas for the corresponding arsenic compound 2b only one stable isomer is found. The bis ‐borane adduct t Bu 2 (BH 3 )As‐N(H)‐As(BH 3 ) t Bu 2 ( 3b ) is a rare example of a structurally characterized, tertiary arsine borane adduct, which can be directly compared with the corresponding phosphorus compound t Bu 2 (BH 3 )P‐N(H)‐P(BH 3 ) t Bu 2 ( 3a ). Deprotonation of mixtures containing 2a by n BuLi leads to the lithium‐containing coordination polymer 4a , in which the actual chain consists only of non‐carbon atoms.