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Neutral Formazan Ligands Bound to the fac-(CO)₃Re(I) Fragment: Structural, Spectroscopic, and Computational Studies.

ABSTRACT: Metal complexes with ligands that coordinate via the nitrogen atom of azo (N═N) or imino (C═N) groups are of interest due to their π-acceptor properties and redox-active nature, which leads to interesting (opto)electronic properties and reactivity. Here, we describe the synthesis and characterization of rhenium(I) tricarbonyl complexes with neutral N,N-bidentate formazans, which possess both N═N and C═N fragments within the ligand backbone (Ar¹-NH-N═C(R³)-N═N-Ar⁵). The compounds were synthesized by reacting equimolar amounts of [ReBr(CO)₅] and the corresponding neutral formazan. X-ray crystallographic and spectroscopic (IR, NMR) characterization confirmed the generation of formazan-type species with the structure fac-[ReBr(CO)₃(κ²-N²,N⁴(Ar¹-N¹H-N²═C(R³)-N³═N⁴-Ar⁵))]. The formazan ligand coordinates the metal center in the 'open' form, generating a five-membered chelate ring with a pendant NH arm. The electronic absorption and emission properties of these complexes are governed by the presence of low-lying π*-orbitals on the ligand as shown by DFT calculations. The high orbital mixing between the metal and ligand results in photophysical properties that contrast to those observed in fac-[ReBr(CO)₃(L,L)] species with α-diimine ligands.

SUBMITTER: Capulin Flores L

PROVIDER: S-EPMC9438031 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

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Neutral Formazan Ligands Bound to the fac-(CO)3Re(I) Fragment: Structural, Spectroscopic, and Computational Studies.

Capulín Flores Liliana L Paul Lucas A LA Siewert Inke I Havenith Remco R Zúñiga-Villarreal Noé N Otten Edwin E

Inorganic chemistry 20220815 34

Metal complexes with ligands that coordinate via the nitrogen atom of azo (N═N) or imino (C═N) groups are of interest due to their π-acceptor properties and redox-active nature, which leads to interesting (opto)electronic properties and reactivity. Here, we describe the synthesis and characterization of rhenium(I) tricarbonyl complexes with neutral N,N-bidentate formazans, which possess both N═N and C═N fragments within the ligand backbone (Ar1-NH-N═C(R3)-N═N- ...[more]

PMID: 35969867

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Project description:Treatment of two precursors, fac-[Re(CO)(3)(L)(CH(3)CN)]BF(4) [L = 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me(2)bipy) (1) and 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me(2)bipy) (2)], with five C(2)-symmetrical saturated heterocyclic amines yielded 10 new amidine complexes, fac-[Re(CO)(3)(L)(HNC(CH(3))N(CH(2)CH(2))(2)Y)]BF(4) [Y = CH(2), (CH(2))(2), (CH(2))(3), NH, or O]. All 10 complexes possess the novel feature of having only one isomer (amidine E configuration), as established by crystallographic and (1)H NMR spectroscopic methods. We are confident that NMR signals of the other possible isomer (amidine Z configuration) would have been detected, if it were present. Isomers are readily detected in closely related amidine complexes because the double-bond character of the amidine C-N3 bond (N3 is bound to Re) leads to slow E to Z isomer interchange. The new fac-[Re(CO)(3)(L)(HNC(CH(3))N(CH(2)CH(2))(2)Y)]BF(4) complexes have C-N3 bonds with essentially identical double-bond character. However, the reason that the Z isomer is so unstable as to be undetectable in the new complexes is undoubtedly because of unfavorable clashes between the equatorial ligands and the bulky N(CH(2)CH(2))(2)Y ring moiety of the axial amidine ligand. The amidine formation reactions in acetonitrile (25 °C) proceeded more easily with 2 than with 1, indicating that the distortion in 6,6'-Me(2)bipy resulting from the proximity of the methyl substituents to the inner coordination sphere enhanced the reactivity of the coordinated CH(3)CN. Reaction times for 1 and 2 exhibited a similar dependence on the basicity and ring size of the heterocyclic amine reactants. Moreover, when the product of the reaction of 1 with piperidine, fac-[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH(3))N(CH(2)CH(2))(2)CH(2))]BF(4), was challenged in acetonitrile-d(3) or CDCl(3) with a 5-fold excess of the strong 4-dimethylaminopyridine ligand, there was no evidence for replacement of the amidine ligand after two months, thus establishing that the piperidinylamidine ligand is a robust ligand. This chemistry offers promise as a suitable means for preparing isomerically pure conjugated fac-[(99m)Tc(CO)(3)L](n±) imaging agents, including conjugates with known bioactive heterocyclic amines.

Project description:We study Re analogues of (99m)Tc renal agents to interpret previous results at the (99m)Tc tracer level. The relative propensities of amine donors versus carboxylate oxygen donors of four L = polyaminocarboxylate ligands to coordinate in fac-[Re(I)(CO)(3)L](n) complexes were assessed by examining the reaction of fac-[Re(I)(CO)(3)(H(2)O)(3)](+) under conditions differing in acidity and temperature. All four L [N,N-bis-(2-aminoethyl)glycine (DTGH), N,N-ethylenediaminediacetic acid, diethylenetriamine-N-malonic acid, and diethylenetriamine-N-acetic acid] can coordinate as tridentate ligands while creating a dangling chain terminated in a carboxyl group. Dangling carboxyl groups facilitate renal clearance in fac-[(99m)Tc(I)(CO)(3)L](n) agents. Under neutral conditions, the four ligands each gave two fac-[Re(I)(CO)(3)L](n) products with HPLC traces correlating well with known traces of the fac-[(99m)Tc(I)(CO)(3)L](n) mixtures. Such mixtures are common in renal agents because the needed dangling carboxyl group can compete for a coordination site. However, the HPLC separations needed to assess the biodistribution of a single tracer are impractical in a clinical setting. One goal in investigating this Re chemistry is to identify conditions for avoiding this problem of mixtures in preparations of fac-[(99m)Tc(I)(CO)(3)L](n) renal tracers. After separation and isolation of the fac-[Re(I)(CO)(3)L](n) products, NMR analysis of all products and single crystal X-ray crystallographic analysis of both DTGH products, as well as one product each from the other L, allowed us to establish coordination mode unambiguously. The product favored in acidic conditions has a dangling amine chain and more bound oxygen. The product favored in basic conditions has a dangling carboxyl chain and more bound nitrogen. At the elevated temperatures used for simulating tracer preparation, equilibration was facile (ca. 1 h or less), allowing selective formation of one product by utilizing acidic or basic conditions. The results of this fundamental study offer protocols and guidance useful for the design and preparation of fac-[(99m)Tc(I)(CO)(3)L](n) agents consisting of a single tracer.

Dataset Information

Neutral Formazan Ligands Bound to the fac-(CO)₃Re(I) Fragment: Structural, Spectroscopic, and Computational Studies.

Publications

Neutral Formazan Ligands Bound to the <i>fac</i>-(CO)<sub>3</sub>Re(I) Fragment: Structural, Spectroscopic, and Computational Studies.

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