Abstract
[TcI(NO)Cl(H2L1)2]+ cations (H2L1 = 2‐(diphenylphosphanyl)aniline) are formed during reactions of H2L1 with (NBu4)[Tc(NO)Cl4(MeOH)] or (NH4)TcO4/HCl/NH2OH mixtures. Different isomers were isolated depending on the counterions and solvents used. The technetium(I) complexes cis‐NO,Cl,trans‐P,P‐[TcI(NO)Cl(H2L1)2]Cl, trans‐NO,Cl,cis‐P,P‐[TcI(NO)Cl(H2L1)2]2(TcCl6), and trans‐NO,Cl,trans‐P,P‐[TcI(NO)Cl(H2L1)2](PF6) were isolated in crystalline form and studied by spectroscopic methods and X‐ray crystallography. DFT calculations show that there are only minor energy differences between the three isomers and the formation of the individual compounds is most probably strongly influenced by interactions with solvents and counterions.
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