Mononuclear Indium and Gallium Tetrachlorocatecholate Complexes

Lawson, YG; Norman, N. C.; Orpen, A. Guy; Quayle, Michael J.

doi:10.1107/s0108270197010901

Cited by 4 publications

(3 citation statements)

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“…The solid-state structure of 12 is isostructural with that of 10 , as shown in Figure with selected bond lengths and angles provided in Table . The bond lengths about the gallium atom are slightly shorter when compared with the related compound GaCl(1,2-O 2 C 6 Cl 4 )(py)(phen) (py = C 5 H 5 N, phen = 1,10-phenanthroline) (Ga−O = 1.952(4) Å, Ga−N py = 2.155(4) Å, Ga−Cl = 2.329(2) Å) but remain consistent with those of other crystallographically characterized six-coordinate Ga(III) compounds 6 Thermal ellipsoid (50%) plot of 12 .…”

Section: Resultssupporting

confidence: 79%

“…The bond lengths about the gallium atom are slightly shorter when compared with the related compound GaCl(1,2-O 2 C 6 Cl 4 )(py)(phen) (py ) C 5 H 5 N, phen ) 1,10phenanthroline) (Ga-O ) 1.952(4) Å, Ga-N py ) 2.155(4) Å, Ga-Cl ) 2.329(2) Å) but remain consistent with those of other crystallographically characterized six-coordinate Ga-(III) compounds. 74 Uranium. Reaction of UI 3 (THF) 4 with K(BPPA) led to the subsequent isolation of the product 13 in relatively low yield, presumably Via disproportionation of the metal.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Reactivity of Metal Complexes Supported by the Tetradentate Monoanionic Ligand Bis(2-picolyl)(2-hydroxy-3,5-di-tert-butylbenzyl)amide (BPPA)

et al. 2007

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Metal-halide complexes of Ti, V, Y, Zr, Al, Ga, and U supported by the tetradentate monoanionic (TDMA) ligand bis(2-picolyl)(2-hydroxy-3,5-di-tert-butylbenzyl)amine, H(BPPA), were synthesized and spectroscopically characterized. In addition, the complexes (BPPA)TiCl2, (BPPA)VBr2, [(BPPA)YCl2]2, (BPPA)AlCl2, (BPPA)GaCl2, and (BPPA)UI3 were characterized by single-crystal X-ray crystallography. In all cases the ligand is bound kappa4 to the metal center. All structurally characterized compounds are monomeric in the solid-state with the exception of [(BPPA)YCl2]2, which exists as a dimer in the solid-state. The metal-alkyl complexes (BPPA)AlMe2 and (BPPA)Zr(CH2Ph)3 were also synthesized and characterized, and an X-ray structure of (BPPA)Zr(CH2Ph)3 was obtained. The transformation of BPPA from a monoanionic to a dianionic ligand via proton abstraction was observed and monitored by NMR spectroscopy.

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Section: Resultssupporting

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of Metal Complexes Supported by the Tetradentate Monoanionic Ligand Bis(2-picolyl)(2-hydroxy-3,5-di-tert-butylbenzyl)amide (BPPA)

et al. 2007

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“…Unfortunately, the authors6,10a did not produce sufficient evidence of such structures, and the last ones are questionable. Moreover, the minor product obtained in the reaction of Cl 4 Q with Ga in the presence of phen is the structurally characterized monomeric complex (Cl 4 Cat)GaCl · py · phen (py = pyridine) 10b. It indicates the more complicated nature of the interaction of metallic gallium with Hal 4 Q , which includes elimination of halides from the initial o ‐quinone.…”

Section: Introductionmentioning

confidence: 99%

The Reduction of Sterically Hindered o‐Quinone and o‐Iminoquinone with Gallium and “GaI”

et al. 2012

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Keywords: Gallium / Quinones / Reduction / EPR spectroscopyMetallic gallium reacts with 3,6-di-tert-butyl-o-benzoquinone (3,6-Q) in THF to produce a gallium tris-o-semiquinolate complex, whereas the same interaction with 4,6di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (imQ) does not proceed. The reduction of imQ is possible with amalgamed gallium in THF and produces a gallium complex that contains two o-iminobenzoquinone ligands in different redox states. In the case of 3,6-Q, the analogous reaction leads to dimeric derivative [Cat 2 Ga(Et 2 O) 2 ]-[a] G.A. Razuvaev 4318[CatGa] (in which Cat is the dianion of 3,6-Q). The structure of this compound was determined by X-ray diffraction analysis. The gallium(III) amidophenolate derivative can only be obtained by exchange reaction of APNa 2 with GaI 3 (in which AP is the dianion of imQ). The reduction of 3,6-Q and imQ with "GaI" results in the formation of corresponding compounds that contain redox-active ligands in the dianionic state. The structure of [AP 2 Ga][GaI 2 ] was determined by Xray diffraction analysis. Scheme 1. The reaction of digallane with alkynes.o-Quinone and o-Iminoquinone with Gallium and "GaI" One of the most convenient methods of synthesis of metal complexes with redox-active ligands is the direct reduction of o-quinones and their hetero-analogues by metals or metal amalgams. [8] (BIAN)Ga-Ga(BIAN) [9a] and the tris-o-semiquinolate gallium(III) derivatives that contain different o-quinones were synthesized by this method. [6,9b-9d] In some cases, the direct interaction of quinones with gallium leads to the formation of the respective dianionic catecholate derivatives. As reported in the literature, [6] heating of the gallium metal with 1,2-naphthoquinone (NQ) in refluxing toluene results in a deeper reduction of NQ and gives the dimeric catecholate complex [Ga II -(NCat)] 2 (NCat is the dianion of NQ). Catecholate gallium derivatives [(Hal 4 Cat)Ga II ·(phen)] 2 (Hal 4 Cat are dianions of tetrahalo-substituted o-quinones Hal 4 Q; phen = 1,10phenanthroline) form as the result of the reaction of metal with quinones in the presence of phen. [10a] Unfortunately, the authors [6,10a] did not produce sufficient evidence of such structures, and the last ones are questionable. Moreover, the minor product obtained in the reaction of Cl 4 Q with Ga in the presence of phen is the structurally characterized monomeric complex (Cl 4 Cat)GaCl·py·phen (py = pyridine). [10b] It indicates the more complicated nature of the interaction of metallic gallium with Hal 4 Q, which includes elimination of halides from the initial o-quinone.Low-oxidation-state metal derivatives are widely known to reduce 1,2-diketones and related ligands to give chelated compounds with reduced forms of the redox-active ligands. Thus the interaction of benzil with "GaI" results in the formation of a novel trimetallic bis(enediolato) complex. [11a] "GaI" was shown to be a convenient initial reagent for the synthesis of α-diimine gallium derivatives. [11b-11e] The reducti...

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2,2′-Bipyridine,1,10-phenanthroline and 2,2′:6′,2″-terpyridine in gallium(III) chemistry: Complexes containing the core

Papaefstathìou

Sofetis

Raptopoulou

et al. 2007

Journal of Molecular Structure

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Mononuclear Indium and Gallium Tetrachlorocatecholate Complexes

Cited by 4 publications

References 3 publications

Synthesis and Reactivity of Metal Complexes Supported by the Tetradentate Monoanionic Ligand Bis(2-picolyl)(2-hydroxy-3,5-di-tert-butylbenzyl)amide (BPPA)

Synthesis and Reactivity of Metal Complexes Supported by the Tetradentate Monoanionic Ligand Bis(2-picolyl)(2-hydroxy-3,5-di-tert-butylbenzyl)amide (BPPA)

The Reduction of Sterically Hindered o‐Quinone and o‐Iminoquinone with Gallium and “GaI”

2,2′-Bipyridine,1,10-phenanthroline and 2,2′:6′,2″-terpyridine in gallium(III) chemistry: Complexes containing the core

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