The aminorhenium complex (CO)2ReNH(CH3)CH2CH2(η5-C5H4) (3), in which the ligating amino group is connected to the cyclopentadienyl ligand, was prepared by irradiation of (η5-C5H4CH2CH2NHCH3)Re(CO)3 (2) in THF. Alkylation of the corresponding anion [(CO)2ReN(CH3)CH2CH2(η5-C5H4)]-Li+ (4) as well as the neutral aminorhenium complex 3 with a variety of electrophiles has been studied. The anion 4 reacted with electrophiles, such as CH3I, CH2CHCH2Br, C6H5CH2Br, and HC⋮CCH2Br, at the nitrogen center to provide (CO)2ReNR(CH3)CH2CH2(η5-C5H4) (5a−d). However, 4 reacted with electrophiles having a carbonyl group or a nitrile group next to the electrophilic carbon, such as BrCH2CO2CH3, BrCH2CO2C2H5, and BrCH2CN, to give rhenium alkylation compounds [(CO)2(R)ReNH(CH3)CH2CH2(η5-C5H4)]+Br- (7e−g) after protonation. The neutral aminorhenium complex 3 reacted with the electrophiles mentioned above to provide exclusive Re-alkylation compounds 7a−g. The structure of the tetraphenylborate salt of 7c, [(CO)2(C6H5CH2)ReNH(CH3)CH2CH2(η5-C5H4)]+BPh4 - (8), has been determined by X-ray diffraction.

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