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. 2025 Aug 19;44(17):1965-1976.
doi: 10.1021/acs.organomet.5c00250. eCollection 2025 Sep 8.

Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m‑Terphenyl IsocyanidesSteric Bulk Matters

Domenik Nowak  1 , Guilhem Claude  1 , Anna-Maria Tsirigoni  1 , Adelheid Hagenbach  1 , Joshua S Figueroa  2 , Ulrich Abram  1
Affiliations

Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m‑Terphenyl IsocyanidesSteric Bulk Matters

Domenik Nowak et al. Organometallics. .

Abstract

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.

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Figures

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1. Common Precursor Molecules for the Synthesis of Thionitrosyl Complexes
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2. m-Terphenyl Isocyanides Used Throughout This Study
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1. Syntheses of ReV and TcV Nitrido Complexes with m-Terphenyl Isocyanides
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3. Previously Studied Nitridotechnetium­(V) Complexes with CNArDipp2 and CNArMes2
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2. Dimeric Technetium Complex Isolated from a Reaction of [TcNCl2(PPh3)2] with CN t Bu
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1
Molecular structures of (a) trans-[ReNCl2(CNArTripp2)2(MeOH)] (1), (b) mer,cis-[ReNCl2(CNArMes2)3] (3), and (c) [{TcCl­(CN t Bu)4}2(μ-N)]+ cation of compound 5. Thermal ellipsoids represent 50% probability.
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3. Syntheses of Thionitrosylrhenium and -Technetium Complexes with Sterically Encumbered m-Terphenyl Isocyanides
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2
Liquid (a) and frozen (b) solution X-band EPR spectra of [Tc­(NS)­Cl3(CNArTripp2)2] (9) in CH2Cl2.
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Molecular structures of (a) trans-[Re­(NS)­Cl3(CNArTripp2)2] (6), (b) trans-[Re­(NS)­Cl3(CNArDipp2)2] (7), (c) trans-[Tc­(NS)­Cl3(CNArTripp2)2] (9), and (d) trans-[Tc­(NS)­Cl3(CNArDipp2)2] (10). Thermal ellipsoids represent 30% probability.
4
4
Ellipsoid plot of the molecular structure of [{Tc­(NS)­Cl­(CNArMes2)2}2Cl2] (12). Thermal ellipsoids represent 50% probability. Selected bond lengths (Å) and angles (°): Tc–C1:1.996(6), Tc–C2:1.993(5), C1–N1:1.159(7), C2–N2:1.149(7), Tc–N10:1.77(1), N10–S10:1.54(1), Tc–N10–S10:175.2(16), Tc–C1–N1:177.9(5), Tc–C2–N2:175.5(4), Tc–Cl2–Tc′: 95.43(4), Cl2–Tc–Cl2′: 84.58(4), Tc···Tc′: 3.673. Symmetry code: 1 – x, y, 1 – z.
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Side views and top views of space-filling models of the rhenium complexes 7 (a) and 6 (b) illustrate the degree of steric shielding due to the CNArDipp2 and CNArTripp2 ligands. Overlay of both structures (c), where the CNArDipp2 ligands are shown in red and the CNArTripp2 ligand in gray. The spheres represent each 75% of the van der Waals radii of the atoms.
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6
Space-filling model of the CNArMes2 complex 3 in front view (a) and back view (b).
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