Pathway of Addition Reactions in Tetrasila-2-Phospha-1-Tetrazene

Abstract

Tetrakis(trimethylsilyl)-2-phospha-l-tetrazene (Me 3 Si)7N-N(SiMe 3 )-P=N(SiMe 3 ), (1) reacts with an alkyllithium RLi (R=Me, Bu) to form the P(IlI)amide (Me 3 Si) 2 N-N(SiMe 3 )-P(R)-N(SiMe 3 )Li which undergoes an intramolecular rearrangement at room temperature to give the imino-phosphoranide (Me 3 Si) 2 N-N(SiMe 3 )-P(R)(Li)=NSiMe·;. The phosphoramide as well as the imino-phosphoranide react with Me 3 ECl (E=Si,Sn) to form the phosphine (Me 3 Si) 2 N-N(SiMe 3 )-P(Me)-N(SiMe 3 )(EMe 3 ) and the phosphorane (Me 3 Si) 2 N-N(SiMe 3 )-P(Bu)(EMe 3 )=N(SiMe 3 ),respectively. The former undergoes a slow rearrangement to form a phosphorane, whereas the latter is stable.

Silyl stabilized azanes: reactions of lithiumbis(trimethylsilyl)hydrazine with trialkyltin halides

“…If the lithium atom of lithiumbis(trimethylsilyl)hydrazine, 1a, is substituted by an -SnR 3 group, the resulting (trialkylstannyl)bis(trimethylsilyl)hydrazine, 2, would be endowed with two differentially reactive N-H and N-Sn bonds. As part of our study on silyl-nitrogen compounds [7][8][9][10], we report herein the reactions of lithiumbis(trimethylsilyl)hydrazine, Li(H)N 2 (SiMe 3 ) 2 , 1a, with trialkyltin halides.…”