Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNArTripp2, CNArDipp2, and CNArMes2 (Tripp = 2,4,6-triisopropylphenyl, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) have been synthesized by reactions of the corresponding nitridotechnetium(V) or rhenium(V) compounds with disulfur dichloride. The structures of the products and the oxidation states of the resulting metal ions are mainly controlled by the steric bulk of the terphenyl isocyanide ligands. Bis(isocyanide) Tc(II) and Re(II) were obtained exclusively with CNArTripp2 or CNArDipp2, which is in contrast with the more diverse reaction outcomes with the less bulky CNArMes2, where the products also include metal(I) and dimeric compounds. The obtained complexes [ReVNCl2(CNArTripp2)2(MeOH)], [ReVNCl2(CNArDipp2)2], [ReVNCl2(CNArMes2)3], [TcVNCl2(CNArTripp2)2], [ReII(NS)Cl3(CNArTripp2)2], [ReII(NS)Cl3(CNArDipp2)2], [ReI(NS)Cl2(CNArMes2)3], [TcII(NS)Cl3(CNArTripp2)2], [TcII(NS)Cl3(CNArDipp2)2], [TcII(NS)Cl2(CNArMes2)3]Cl, and [{Tc(NS)Cl(CNArMes2)2}2Cl2] were studied spectroscopically and partially by X-ray diffraction.
