Nuclearity manipulation in Schiff-base fac-tricarbonyl complexes of Mn(I) and Re(I)

Mokolokolo, Pennie P.; Frei, Angelo; Tsosane, Mampotso S.; Kama, Dumisani V.; Schutte‐Smith, Marietjie; Brink, Alice; Visser, Hendrik G.; Meola, Giuseppe; Alberto, Roger; Roodt, Andreas

doi:10.1016/j.ica.2017.10.036

Cited by 20 publications

(18 citation statements)

References 77 publications

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“…This is in agreement with other rhenium and manganese structures whereby overlay diagrams and isostructural compounds indicate this preference for an invariable structure (Mokolokolo et al, 2017). This is unexpected since, in the case of Mokolokolo et al, the ligands coordinate in a bidentate fashion, the ligands are symmetrical in the compounds formed and the peripheral ligands lie staggered with respect to each other, whereas the structures reported here vary from two to three sulfur-bridged compounds; in (1), there is one ligand per cluster and in (2) there are three ligands per cluster and the ligands are nonsymmetrical in the compounds.…”

Section: X-ray Crystallographysupporting

confidence: 91%

“…With respect to dinuclear species, one has the option of introducing two similar or different biologically active molecules. Dinuclear structures of manganese and rhenium, comparable to the reported structures, have been reported, with O atoms from Schiff base ligands forming the bridges between the metal centres (Mokolokolo et al, 2017). In effect, mixed-metal complexes could be synthesized, for example, Re-99m Tc complexes.…”

Section: Introductionsupporting

confidence: 67%

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Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

et al. 2018

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The synthesis and characterization of two dinuclear complexes, namely fachexacarbonyl-1 3 C,2 3 C-(pyridine-1N)[-2,2 0 -sulfanediyldi(ethanethiolato)-1 2 S 1 ,S 3 :2 3 S 1 ,S 2 ,S 3 ]dirhenium(I), [Re 2 (C 4 H 8 S 3 )(C 5 H 5 N)(CO) 6 ], (1), and tetraethylammonium fac-tris(-2-methoxybenzenethiolato-2 S:S)bis[tricarbonylrhenium(I)], (C 8 H 20 N)[Re 2 (C 7 H 7 OS) 3 (CO) 6 ], (2), together with two mononuclear complexes, namely (2,2 0 -bithiophene-5-carboxylic acid-2 S,S 0 )bromidotricarbonylrhenium(I), (3), and bromidotricarbonyl(methyl benzo[b]thiophene-2-carboxylate-2 O,S)rhenium(I), (4), are reported. Crystals of (1) and (2) were characterized by X-ray diffraction. The crystal structure of (1) revealed two Re-S-Re bridges. The thioether S atom only bonds to one of the Re I metal centres, while the geometry of the second Re I metal centre is completed by a pyridine ligand. The structure of (2) is characterized by three S-atom bridges and an ReÁ Á ÁRe nonbonding distance of 3.4879 (5) Å , which is shorter than the distance found for (1) [3.7996 (6)/3.7963 (6) Å ], but still clearly a nonbonding distance. Complex (1) is stabilized by six intermolecular hydrogen-bond interactions and an OÁ Á ÁO interaction, while (2) is stabilized by two intermolecular hydrogen-bond interactions and two OÁ Á Á interactions.

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Section: X-ray Crystallographysupporting

confidence: 91%

Section: Introductionsupporting

confidence: 67%

Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

et al. 2018

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“…The geometric distortion around the Re I core is best illustrated by the bond angles around the Re I centre, with the largest deviation from 90 found for O11-Re1-O12, with a reported value of 76.78 7. The bond lengths and angles are within the ranges reported for similar structures (Gö ttlicher & Ochsenreiter, 1974;Cheng et al, 1999;Schutte et al, 2011Schutte et al, , 2012Mokolokolo et al, 2017;Manicum et al, 2015Manicum et al, , 2018Twala et al, 2015), as well as for the free molecule (Podlaha et al, 2014). Selected bond lengths and angles for 1 are summarized in Table 2 and the molecular diagram with the atom-numbering scheme is given in Fig.…”

Section: X-ray Crystallographysupporting

confidence: 82%

“…This could be due to the small O4-Re1-O5 bite angle of 76.72 (9) . All the bond lengths and angles are in the normal ranges compared to similar compounds (Speier et al, 1990;Balogh-Hergovich et al, 1991;Sun et al, 2014;Annan et al, 1990;Schutte et al, 2011Schutte et al, , 2012Mokolokolo et al, 2017;Manicum et al, 2015Manicum et al, , 2018Twala et al, 2015). The ReÁ Á ÁRe nonbonding distance is 5.114 (7) Å .…”

Section: 4mentioning

confidence: 90%

Structures of rhenium(I) complexes with 3-hydroxyflavone and benzhydroxamic acid as O,O′-bidentate ligands and confirmation of π-stacking by solid-state NMR spectroscopy

et al. 2019

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The synthesis and crystal structures of two new rhenium(I) complexes obtained utilizing benzhydroxamic acid (BHAH) and 3-hydroxyflavone (2-phenylchromen-4-one, FlavH) as bidentate ligands, namely tetraethylammonium fac-(benzhydroxamato-κ2 O,O′)bromidotricarbonylrhenate(I), (C8H20N)[ReBr(C7H6NO2)(CO)3], 1, and fac-aquatricarbonyl(4-oxo-2-phenylchromen-3-olato-κ2 O,O′)rhenium(I)–3-hydroxyflavone (1/1), [Re(C15H9O3)(CO)3(H2O)]·C15H10O3, 3, are reported. Furthermore, the crystal structure of free 3-hydroxyflavone, C15H10O3, 4, was redetermined at 100 K in order to compare the packing trends and solid-state NMR spectroscopy with that of the solvate flavone molecule in 3. The compounds were characterized in solution by 1H and 13C NMR spectroscopy, and in the solid state by 13C NMR spectroscopy using the cross-polarization magic angle spinning (CP/MAS) technique. Compounds 1 and 3 both crystallize in the triclinic space group P\overline{1} with one molecule in the asymmetric unit, while 4 crystallizes in the orthorhombic space group P212121. Molecules of 1 and 3 generate one-dimensional chains formed through intermolecular interactions. A comparison of the coordinated 3-hydroxyflavone ligand with the uncoordinated solvate molecule and free molecule 4 shows that the last two are virtually completely planar due to hydrogen-bonding interactions, as opposed to the former, which is able to rotate more freely. The differences between the solid- and solution-state 13C NMR spectra of 3 and 4 are ascribed to inter- and intramolecular interactions. The study also investigated the potential labelling of both bidentate ligands with the corresponding fac-99mTc-tricarbonyl synthon. All attempts were unsuccessful and reasons for this are provided.

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“…The complexity of the synthesis of multi-nuclear complexes has hindered interest in medical use. However, the reactivity studies on manganese(I) tricarbonyl complexes have provided insight into the manner in which the nuclearities of rhenium(I) tricarbonyl complexes can be manipulated to form either mono-or dinuclear species (Mokolokolo et al, 2018). This has been followed by two strategies which can prepare multinuclear rhenium(I) and technetium(I) tricarbonyl complexes, either di-or tetranuclear clusters, in a one-pot reaction.…”

Section: Introductionmentioning

confidence: 99%

Formation of a highly dense tetra-rhenium cluster in a protein crystal and its implications in medical imaging

Brink

Helliwell

2019

Int Union Crystallogr J

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The fact that a protein crystal can serve as a chemical reaction vessel is intrinsically fascinating. That it can produce an electron-dense tetranuclear rhenium cluster compound from a rhenium tricarbonyl tribromo starting compound adds to the fascination. Such a cluster has been synthesized previously in vitro, where it formed under basic conditions. Therefore, its synthesis in a protein crystal grown at pH 4.5 is even more unexpected. The X-ray crystal structures presented here are for the protein hen egg-white lysozyme incubated with a rhenium tricarbonyl tribromo compound for periods of one and two years. These reveal a completed, very well resolved, tetra-rhenium cluster after two years and an intermediate state, where the carbonyl ligands to the rhenium cluster are not yet clearly resolved, after one year. A dense tetranuclear rhenium cluster, and its technetium form, offer enhanced contrast in medical imaging. Stimulated by these crystallography results, the unusual formation of such a species directly in an in vivo situation has been considered. It offers a new option for medical imaging compounds, particularly when considering the application of the pre-formed tetranuclear cluster, suggesting that it may be suitable for medical diagnosis because of its stability, preference of formation and biological compatibility.

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Nuclearity manipulation in Schiff-base fac-tricarbonyl complexes of Mn(I) and Re(I)

Cited by 20 publications

References 77 publications

Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

Structures of rhenium(I) complexes with 3-hydroxyflavone and benzhydroxamic acid as O,O′-bidentate ligands and confirmation of π-stacking by solid-state NMR spectroscopy

Formation of a highly dense tetra-rhenium cluster in a protein crystal and its implications in medical imaging

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Nuclearity manipulation in Schiff-base fac-tricarbonyl complexes of Mn(I) and Re(I)

Cited by 20 publications

References 77 publications

Synthesis of ReItricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two ReIdinuclear structures bridged by S atoms

Synthesis of ReItricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two ReIdinuclear structures bridged by S atoms

Structures of rhenium(I) complexes with 3-hydroxyflavone and benzhydroxamic acid as O,O′-bidentate ligands and confirmation of π-stacking by solid-state NMR spectroscopy

Formation of a highly dense tetra-rhenium cluster in a protein crystal and its implications in medical imaging

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Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms