Boron diamide derivatives containing N-N and N-P molecular fragments.

The cationic and neutral boron-diamide precursors are employed to target the inclusion of N 2 and N-P molecular fragments. The species (HCN(Dipp)) 2 BNH 2 5, and (H 2 CN(Dipp)) 2 BNH 2 6 were prepared. While efforts to oxidize with [NO] + gave mixtures of products, reactions with N 2 H 4 gave the salts [(HCN(Dipp)) 2 B(NHNH 3 )][O 3 SCF 3 ] 7 [(H 2 CN(Dipp)) 2 B(NHNH 3 )][O 3 SCF 3 ] 8. Excess N 2 H 4 gave the neutral species (HCN(Dipp)) 2 B(NHNH 2 ) 9 and (H 2 CN(Dipp)) 2 B(NHNH 2 ) 10, respectively. The species (H 2 CN(Dipp)) 2 B(N 3 ) 11 was prepared for comparative purposes. Turning to related NP species, compound 6 was converted to (HCN(Dipp)) 2 B(NHPCl 2 ) 12, while (HCN(Dipp)) 2 BNK(SiMe 3 ) 14 was used to give (HCN(Dipp)) 2 BN(SiMe 3 )PCl 2 15. Replacement of one of the chlorides gave (HCN(Dipp)) 2 BN(SiMe 3 )PCl(OSO 2 CF 3 ) 16 which converts to [(HCN(Dipp)) 2 BNPCl] 2 17. Similarly heating 15 afforded 17. The insights for the synthesis of further boron-N 2 and boron-NP derivatives are discussed.