Main group (IIIA or 13) complexes of benzohydroxamic acid and the crystal structure of tris(benzohydroxamato)indium(III)

Matsuba, Carey A; Rettig, Steven J.; Orvig, Chris

doi:10.1139/v88-292

Cited by 8 publications

(6 citation statements)

References 18 publications

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“…The robust formation of identical Ga/In-(hydroxamate) 3 nodes in these MOMs suggested that these moieties were stable and favored, concurring with previously reported hydroxamate-chelated Group 13 metal complexes. 37,38 Moreover, similar phenomena were recorded in the MOF literature where identical PBUs/SBUs could be interconnected by ligands of the same basic geometry to form diverse topologies. 39−42 For SUM-82, NH 3 •H 2 O was a key factor in the reaction between In(NO 3 ) 3 •4.5H 2 O and H 2 -TDHA when used as a modulator (Figure 3a).…”

Section: ■ Results and Discussionsupporting

confidence: 65%

Structural Diversity in Ga/In-Hydroxamate Metal–Organic Materials

Wu,

Qin,

Duan

et al. 2024

Inorg. Chem.

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Developing metal–organic materials (MOMs) with chemical robustness is a prerequisite to exploring their intriguing properties and applications. As part of a continuing effort to construct robust MOMs featuring chelated building units, here we introduce a “bent” thiophene-2,5-dihydroxamate ligand with multiple intrinsic conformations when it is used as a chelating linkage. This approach should further diversify the coordination chemistry in hydroxamate-based MOM structures without compromising the stability. In combination with Group 13 metals Ga/In to ensure homoleptic metal vertices, we report the successful crystallization of four MOMs with diverse structures and dimensionalities: SUM-81 as a 0D metal–organic polyhedron (MOP), SUM-82 as a 2D MOF with an fes topology, SUM-83 and SUM-84 as distinct 1D coordination polymers with shapes mimic stairs and mesh tubes, respectively. As these structures indeed contain the aforementioned different ligand conformations and combinations thereof, these results expand our understanding of the coordination chemistry of hydroxamates. To demonstrate the potential applicability of hydroxamate-chelated robust MOMs, the permanently porous SUM-81 MOP was successfully incorporated in a series of mixed matrix membranes for CO2/N2 separation, showing impressive performances.

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Section: ■ Results and Discussionsupporting

confidence: 65%

Structural Diversity in Ga/In-Hydroxamate Metal–Organic Materials

Wu,

Qin,

Duan

et al. 2024

Inorg. Chem.

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“…For the corresponding metalate [{Li(THF) 2 } 2 {Li(THF)}{In(( S )-BINOLate) 3 }]·[{Li(THF) 2 }{Li(THF)} 2 {In(( S )-BINOLate) 3 }] 2 · 8toluene a mean value of 2.15 Å was found . Quite similar In−O bond lengths of 2.13−2.15 Å were found in the complexes In(acac) 3 , In[ON(H)C(O)Ph] 3 ·EtOH, and In(1,2-O 2 C 7 H 5 ) 3 , all containing In centers with CN 6. A drastic elongation of the metal−oxygen distances occurred on changing to CN 8.…”

Section: Resultsmentioning

confidence: 73%

BINOL Compounds of Group 13

and

Neumüller

2001

Organometallics

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The reaction of GaMe 3 with 1 equiv of (S)-BINOL ((S)-(-)-2,2′-dihydroxy-1,1′-binaphthyl) in toluene at reflux conditions gave after recrystallization from THF the chiral organogallium alkoxide [(THF)MeGa((S)-BINOLate)] 2 (1). In contrast treatment of PhCH 2 InCl 2 with 1 equiv of Li 2 ((S)-BINOLate) in THF at reflux and recrystallization from DME led not to the desired organoindium alkoxide but to [{(DME)Li} 3 {In((S)-BINOLate) 3 }]‚2DME (2‚2DME). The similar salt [{(DME)Li} 3 {In((S)-BINOLate) 3 }]‚0.75THF (2‚0.75THF) was obtained by direct synthesis of InCl 3 with 3 equiv of Li 2 ((S)-BINOLate) in THF at 65 °C and recrystallization from DME. The compounds 1 and 2 are readily soluble only in donor solvents, while the potassium derivative [{(toluene) 2 K} 3 {In((S)-BINOLate) 3 }]‚2toluene (3‚2toluene), obtained in the reaction of InCl 3 with 3 equiv of K 2 ((S)-BINOLate) in toluene, is very soluble in toluene and n-hexane. 1-3 have been characterized by their NMR, IR, and MS spectra as well as by X-ray analyses. Compound 1 is dimeric with a Ga 2 O 2 four-membered ring. 2 consists of a tetranuclear InO 6 Li 3 skeleton in which every Li + ion is coordinated by one additional DME ligand. The basic structural motif in 3, an InO 6 K 3 core, is comparable to the skeleton in 2. However, the coordinated toluene molecules of every K + ion in 3 are bound by mainly electrostatic metal-π-electron interactions.BINOLate complexes of a variety of metals are very valuable and effective catalysts and reagents for enantioselective synthesis. [1][2][3][4][5][6] Important for the understanding of the respective mechanism is a knowledge of the structure of the BINOLate-metal complexes. Therefore, a number of structural investigations were performed, for example, with Al 1 , Ga, In, 7 Ln, 5 Cr, and Fe. 8 For all of these complexes tetrahedral or octahedral coordination of the central metal was found. For some metals both types are known. It is worth mentioning that at least one coordination site at the central metal should be vacant for a successful enantioselective reaction. 1 However, there are examples as in the enantioselective transfer of MeLi to aldehydes in the presence of [{-(THF) 2 Li} 3 {Ln(BINOLate) 3 }] 5 where the Ln center pos-sesses coordination number 6. So it is not clear whether the coordination number 4 of the central metal is essential or not.We report here a new organometallic gallium-BINO-Late species and three tetranuclear complexes with M 3 O 6 In cores (M ) Li, K), and we focus on the synthesis and structures of the compounds, not on the application in organic synthesis. Experimental SectionGeneral Procedures. All experiments were carried out under an atmosphere of argon using Schlenk techniques. Purification and drying of the solvents were performed using standard methods. 9 GaMe3 was donated by the group of Prof. Dr. J. Lorberth. (S)-(-)-BINOL was purchased from Merck-Schuchardt. PhCH2InCl2 was prepared according to literature procedures. 10 Solvent-free Li2((S)-BINOLate) was prepared by treatment of BINOL ...

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“…The particularly large difference in these complexes is most likely due to the special electronic features of the hydroxypyranone ligand, as the corresponding differences in hydroxypyridin-4-one or hydroxamate are much smaller: 0.03 Å in tris(3-hydroxy-4-pyridinone)indium 32 and 0.02 Å for tris(benzohydroxamato)indium. 33 Accordingly, a quite large difference of 0.055 Å, has been observed for tris-(maltol)aluminum, 34 although in this complex the coordination geometry is meridional.…”

Section: Resultsmentioning

confidence: 87%

Synthesis, Physicochemical Properties, and Biological Evaluation of Hydroxypyranones and Hydroxypyridinones: Novel Bidentate Ligands for Cell-Labeling

A-K

et al. 1996

J. Med. Chem.

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The synthesis of a range of hydroxypyranones and hydroxypyridinones with potential for the chelation of indium(III) is described. The crystal structures of two of the indium complexes are presented. The distribution coefficients of the ligands and the corresponding iron(III), gallium(III), and indium(III) complexes are reported. Good linear relationships between the distribution coefficients of the iron and gallium complexes and iron and indium complexes were obtained. In contrast a nonlinear relationship was obtained between the distribution coefficient of the free ligand and the distribution coefficient of the three groups of complexes. This latter relationship was used to identify compounds with optimal cell labeling properties. Two such compounds both 6-(alkoxymethyl)-3-hydroxy-4H-pyran-4-ones have been compared with tropolone for their ability to label human leucocytes with 111In. The leucocyte labeling efficiencies of the selected ligands were greater and the in-vitro plasma stabilities were similar to that of 111In-tropolonate. These results suggest that the new bidentate ligands may offer advantages over those currently used for cell-labeling.

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Main group (IIIA or 13) complexes of benzohydroxamic acid and the crystal structure of tris(benzohydroxamato)indium(III)

Cited by 8 publications

References 18 publications

Structural Diversity in Ga/In-Hydroxamate Metal–Organic Materials

Structural Diversity in Ga/In-Hydroxamate Metal–Organic Materials

BINOL Compounds of Group 13

Synthesis, Physicochemical Properties, and Biological Evaluation of Hydroxypyranones and Hydroxypyridinones: Novel Bidentate Ligands for Cell-Labeling

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