Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m-Terphenyl Isocyanides─Steric Bulk Matters
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNAr Tripp2, CNAr Dipp2, and CNAr Mes2 (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 Tripp2 or CNAr Dipp2, which is in contrast with the more diverse reaction outcomes with the less bulky CNAr Mes2, where the products also include metal(I) and dimeric compounds. The obtained complexes [Re V NCl 2 (CNAr Tripp2 ) 2 (MeOH)], [Re V NCl 2 (CNAr Dipp2 ) 2 ], [Re V NCl 2 (CNAr Mes2 ) 3 ], [Tc V NCl 2 (CNAr Tripp2 ) 2 ], [Re II (NS)Cl 3 (CNAr Tripp2 ) 2 ], [Re II (NS)Cl 3 (CNAr Dipp2 ) 2 ], [Re I (NS)Cl 2 (CNAr Mes2 ) 3 ], [Tc II (NS)Cl 3 (CNAr Tripp2 ) 2 ], [Tc II (NS)Cl 3 (CNAr Dipp2 ) 2 ], [Tc II (NS)Cl 2 (CNAr Mes2 ) 3 ]Cl, and [{Tc(NS)Cl(CNAr Mes2 ) 2 } 2 Cl 2 ] were studied spectroscopically and partially by X-ray diffraction.
Source: Organometallics
Institutions: Freie Universität Berlin, University of California San Diego
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4413307984