Anions of π‐Acidic N‐nitrosulfonyl/carboxy Amides and Their Re Complexes

The synthesis of the potassium salts of the nitrogen acids N‐nitroamide {N‐nitroacetamide, K[CH 3 C(O)NNO 2 ] ( 1 )}, N‐nitrosulfonamide {N‐nitro‐ p ‐tolylsulfonamide, K[ p ‐tolylSO 2 NNO 2 ] ( 2 )} and N‐nitrocarbamates {N‐nitromethylcarbamate, K[CH 3 OC(O)NNO 2 ] ( 3 ), N‐nitroethylcarbamate, K[C 2 H 5 OC(O)NNO 2 ] ( 4 )} are described. Reaction of 1–4 with [Re(CH 3 CN) 2 (CO) 2 (PPh 3 ) 2 ](X) (X=ClO 4 or BF 4 ) gave the corresponding new Re(I) nitrogen acid complexes Re(η 2 ‐nitrogen acid)(CO) 2 (PPh 3 ) 2 5–8 in good yields. Complex 5 and 6 can also be obtained from the reaction of N‐nitroacetamide ( 1‐H ) or N‐nitro‐ p ‐tolylsulfonamide ( 2‐H ) respectively with the basic Re(I) hydride complex, Re(H)(CO) 2 (PPh 3 ) 3 .