Bis(alkylamino)phosphanes: Deprotonation Reactions and Reactivity oft-BuP(NH-t-Bu)2toward Group 13 Metalloorganics

Reactions of the bis(amino)phosphane t -BuP(NH- t -Bu) 2 with base-stabilized alanes H 3 Al−NR 3 occurred at the “hard” N center with elimination of dihydrogen, yielding [ t -BuP(NH- t -Bu)N( t -Bu)AlH 2 ] 2 ( 1 ), whereas those with boranes, gallanes, and indanes MR 3 (M = B, Ga, In) took place at the “weak” P center, yielding the corresponding phosphane adducts t -Bu(NH- t -Bu) 2 P-MR 3 (MR 3 = BH 3 ( 2 ), GaH 3 ( 3 ), GaMe 3 ( 4 ), InMe 3 ( 5 )). A deprotonation reaction in Et 2 O using an equimolar amount of n -BuLi resulted in the formation of the Li amidophosphane [ t -BuP(NH- t -Bu)N( t -Bu)Li] 2 ( 6 ). 6 adopted a dimeric structure in the solid state but can be converted into its monomeric form by addition of tetramethylethylenediamine (tmeda), yielding t -BuP(NH- t -Bu)N( t -Bu)Li(tmeda) ( 7 ). It is also possible to prepare 7 by a deprotonation reaction with n -BuLi in tmeda. 6 was reacted with GaCl 3 with elimination of LiCl and formation of [ t -BuP(NH- t -Bu)N( t -Bu)GaCl 2 ] x ( 8 ). Compounds 1 − 8 were investigated by means of (multinuclear) NMR ( 1 H, 13 C, 31 P, 7 Li) and IR spectroscopy. In addition, the crystal structures of [ t -BuP(NH- t -Bu)N( t -Bu)AlH 2 ] 2 ( 1 ), t -Bu(NH- t -Bu) 2 P−GaH 3 ( 3 ), [ t -BuP(NH- t -Bu)N( t -Bu)Li] 2 ( 6 ), and t -BuP(NH- t -Bu)N( t -Bu)Li(tmeda) ( 7 ) were determined by single-crystal X-ray diffraction.