Nowak Domenik, Claude Guilhem, Tsirigoni Anna-Maria, Hagenbach Adelheid, Figueroa Joshua S, Abram Ulrich
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Fabeckstr. 34/36, Berlin D-14195, Germany.
Department of Chemistry and Biochemistry, University of California San Diego, 9500 Gilman Drive, MC 0358, La Jolla, California 92093, United States.
Organometallics. 2025 Aug 19;44(17):1965-1976. doi: 10.1021/acs.organomet.5c00250. eCollection 2025 Sep 8.
Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNAr, CNAr, and CNAr (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 CNAr or CNAr, which is in contrast with the more diverse reaction outcomes with the less bulky CNAr, where the products also include metal-(I) and dimeric compounds. The obtained complexes [ReNCl(CNAr)(MeOH)], [ReNCl(CNAr)], [ReNCl(CNAr)], [TcNCl(CNAr)], [Re(NS)-Cl(CNAr)], [Re(NS)-Cl(CNAr)], [Re(NS)-Cl(CNAr)], [Tc(NS)-Cl(CNAr)], [Tc(NS)-Cl(CNAr)], [Tc(NS)-Cl(CNAr)]-Cl, and [{Tc-(NS)-Cl-(CNAr)}Cl] were studied spectroscopically and partially by X-ray diffraction.
锝和铼与大位阻异腈CNAr、CNAr和CNAr（Tripp = 2,4,6 - 三异丙基苯基，Dipp = 2,6 - 二异丙基苯基，Mes = 2,4,6 - 三甲基苯基）形成的低价硫代亚硝酰配合物，是通过相应的氮化锝(V)或铼(V)化合物与二氯化二硫反应合成的。产物的结构以及所得金属离子的氧化态主要由三联苯异腈配体的空间位阻控制。双（异腈）锝(II)和铼(II)仅由CNAr或CNAr制得，这与使用空间位阻较小的CNAr时更多样化的反应结果形成对比，使用CNAr时产物还包括金属(I)和二聚体化合物。对所得到的配合物[ReNCl(CNAr)(MeOH)]、[ReNCl(CNAr)]、[ReNCl(CNAr)]、[TcNCl(CNAr)]、[Re(NS)-Cl(CNAr)]、[Re(NS)-Cl(CNAr)]、[Re(NS)-Cl(CNAr)]、[Tc(NS)-Cl(CNAr)]、[Tc(NS)-Cl(CNAr)]、[Tc(NS)-Cl(CNAr)]-Cl和[{Tc-(NS)-Cl-(CNAr)}Cl]进行了光谱研究，并部分通过X射线衍射进行了研究。
