Functionally Substituted Derivatives of (η⁵-C₅H₅)M(CO)₂NO (M = Cr, Mo, W) Complexes

Compounds of the general type (η⁵-C₆H₄R)M(CO)₂NO have been prepared and their chemistry has been studied, where M = Cr, Mo, and W and R = C0₂CH₃, CHO, COCH₃, C(CH₃)=CH₂, and CH[N(CH₃)₂]CH₃. The carbomethoxy derivatives (R = C0₂CH₃) for all three metals (M = Cr, Mo, W) were obtained in yields of 12-79%. The acetyl (R = COCH₃) and formyl (R = CHO) derivatives were obtained only for M = Cr in yields of 79% and 56%, respectively. The isopropenyl organometallic monomers (R = C(CH₃)=CH₂) have been prepared for molybdenum and tungsten in good yields. Treatment of 6-(dimethylamino)fulvene with methyllithium followed by molybdenum hexacarbonyl and subsequent nitrosylation with N-methyl-N-nitroso-p-toluenesulfonamide gave the (dimethylamino)ethyl derivative (R = CH[N(CH₃)₂]CH₃; M = Mo) in 56% yield. A reaction between lithium nitrocyclopentadienide and chromium hexacarbonyl followed by acetic acid and -Nmethyl-N-nitroso-p-toluenesulfonamide gave the reduced compound (η⁵-C₆H₄NH₂)Cr(CO)₂NO in 7% yield.