Contributions to the Chemistry of Boron, 214. Synthesis and Reaction Chemistry of Aminophosphanylboranes

Aminochlorophosphanylboranes, (R 2 N)B(Cl)P(SiMe 3 ) 2 ( 1a — d ) and (R 2 N)B(Cl)PH 2 ( 2a — d ), are obtained from elimination reactions between aminochloroboranes and LiP(SiMe 3 ) 2 and LiPH 2 , respectively. Selected reaction chemistry of ( i 1‐Pr 2 N)B(Cl)P(SiMe 3 ) 2 ] ( 1a ) with NH 3 , Me 3 SiN 3 , Cr(CO) 5 · NMe 3 , and W(CO) 5 · NMe 3 is described. The azide ( i 1‐Pr 2 N)B(N 3 )P(SiMe 3 ) 2 ( 12a ) is stable at 25°C; however, thermolysis at 80°C provides a novel six‐membered ring compound [( i 1‐Pr 2 N)BN(SiMe 3 )P(SiMe 3 )] 2 ( 13a ). The reaction of (Ph 2 N)B(Cl)P(SiMe 3 ) 2 ( 1b ) with LiP(SiMe 3 ) 2 produces the only isolable bis(phosphanyl)borane ( 5b ), while combination of (R 2 N)B(Cl)Ph 2 with LiPH 2 · DME yields new diphosphadiboretanes 6 {(R 2 N)BPH} 2 (R 2 N i 1‐Pr 2 N, Ph 2 N and tmp2,2,6,6‐tetramethylpiperidino) and triphosphatriborinanes 7 {(R 2 N)BPH} 3 (R 2 N(Me 3 Si) 2 N, Me 2 N and Et 2 N). Two salts, [( i 1‐Pr 2 N) DME] 2 ( 8a ) and [tmpLi · DME] 2 ( 8c ) (DMEethylene glycol dimethyl ether) are also isolated. The results of molecular structure determinations for [( i 1‐Pr 2 N)Bn(SiMe 3 )P(SiMe 3 )] 2 ( 13a ), [tmpBPH] 2 ( 4c ), [tmpBPH] 2 · Cr(CO) 5 ( 7c ), {[(Me 3 Si) 2 N]BPH} 3 ( 4d ), {[(Me 3 Si) 2 N]BPH} 3 · Cr(CO) 5 ( 7d ), (Ph 2 N)B[P(SiMe 3 ) 2 ] 2 ( 5b ), and [( i 1‐Pr 2 N) · DME] 2 ( 8a ) are discussed.