In situ formation of ligand 2,2′-[(E)-diazene-1,2-diyldicarbonothioyl]diphenol and structural characterization of its binuclear rhodium(v) complex containing RhO2+

Gangopadhyay, S.; Basak, Prodyut; Drew, Michael G. B.; Gangopadhyay, P. K.

doi:10.1039/c0cc01970d

Cited by 4 publications

(8 citation statements)

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“…Two reductive eliminations then provide two molecules containing X-S and Y-S bonds, which are accompanied by regeneration of the Rh(I) complex. Formation of Rh(V) complexes has been reported [ 96 , 97 , 98 , 99 ]. A mechanistic model of the insertion reaction can also involve oxidative addition of a Rh(I) complex and a disulfide, which is followed by the transfer of two organothio groups to an unsaturated molecule possessing an X=Y bond to form a product possessing a S-X-Y-S group with the regeneration of the Rh(I) complex ( Figure 7 b).…”

Section: Discussionmentioning

confidence: 99%

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Arisawa

Yamaguchi

2020

Molecules

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Organosulfur compounds are widely used for the manufacture of drugs and materials, and their synthesis in general conventionally employs nucleophilic substitution reactions of thiolate anions formed from thiols and bases. To synthesize advanced functional organosulfur compounds, development of novel synthetic methods is an important task. We have been studying the synthesis of organosulfur compounds by transition-metal catalysis using disulfides and sulfur, which are easier to handle and less odiferous than thiols. In this article, we describe our development that rhodium complexes efficiently catalyze the cleavage of S-S bonds and transfer organothio groups to organic compounds, which provide diverse organosulfur compounds. The synthesis does not require use of bases or organometallic reagents; furthermore, it is reversible, involving chemical equilibria and interconversion reactions.

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Section: Discussionmentioning

confidence: 99%

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Arisawa

Yamaguchi

2020

Molecules

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“…The difference in the side length of two triangular faces arises from the difference in van der Waals radii of S and N and it accounts for the distortion in the trigonal prismatic facial structure. The Mo(1)-N(11) and Mo(1)-S(20) bond lengths are 1.9943 (17) and 2.4191(5) Å, respectively. These bond-lengths are in agreement with those in the tris(thiobenzoyldiazene)molybdenum complex.…”

Section: Crystal Structure Of the Complexesmentioning

confidence: 99%

Thiohydrazide complexes of molybdenum and their relevance to reduction of dinitrogen to ammonia

et al. 2015

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Aqueous solution of sodium molybdate reacts with aromatic thiohydrazides like thiobenzhydrazide, 2-hydroxythiobenzhydrazide, furan-2-thiohydrazide and thiophen-2-thiohydrazide to form green, neutral diamagnetic 1 : 3 chelates. They were characterized by elemental analysis and spectroscopic methods. Tris(2-hydroxythiobenzhydrazido)molybdenum(vi) was crystallized from benzene and the crystal structure shows that molybdenum(vi) is hexacoordinated to three sulfur and three nitrogen atoms from three identical ligands in facile trigonal prismatic geometry. The OH group is involved in intramolecular and intermolecular hydrogen bonding. The bound ligands of tris(thiohydrazido)molybdenum(vi) undergo a redox reaction differently depending on the solvents. Two complexes of molybdenum bound to those oxidized ligands were isolated and characterized and their structures were also solved. Of them a binuclear complex, containing two MoO2(2+) ions, of the ligand N-2-hydroxybenzoyl-N'-2-hydroxythiobenzoylhydrazine showed some capability to catalyze the reduction of dinitrogen to ammonia by sodium borohydride.

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“…Only one previous crystal structure has been reported for a rhodium oxo complex (Figure 4.11). 258 The literature structure contains a rhodium(V) dimer with each rhodium atom coordinated to two oxo ligands, a DMSO ligand and an oxygen-nitrogen-sulfur heterotridentate ligand. The oxo trans to the DMSO ligand has a bond length of 1.701(5) Å, while the oxo trans to the nitrogen donor is slightly longer at 1.712(5) Å.…”

Section: Dioxygen and Oxo Complexesmentioning

confidence: 99%

“…Transition metal oxo complexes have long been studied as they have been implicated to have roles in biological systems, [259][260][261][262] C-H activation 263,264 and various oxidation reactions. 219,265,266 A terminal oxo ligand is a very strong π-donor ligand, thus the strongest coordination occurs with high oxidation state, early tran- 258 sition metals. 267 A review of transition metal oxo complexes published in 1987 stated that "M=O groups are stabilized at metal centres with an oxidation state of no less than +4 and no more than four d electrons".…”

Section: Dioxygen and Oxo Complexesmentioning

confidence: 99%

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Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

Nelson¹

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<p>This thesis provides an account of research into a group of diphosphine ligands with a rigid xanthene backbone and tert -butyl substituents on the phosphorus atoms. The three ligands have different groups in the bridgehead position of the backbone (CMe₂, SiMe₂, or S) which change the natural (calculated) bite-angle of the ligand. The coordination chemistry of these t -Bu-xantphos ligands with late-transition metals has been investigated with a focus on metal complexes that may form in catalytic reactions. The three t -Bu-xantphos ligands were synthesised by lithiation of the backbone using sec -butyllithium/TMEDA and treatment with PtBu₂Cl. The natural biteangles of the Ph-xantphos (111.89–114.18°) and t -Bu-xantphos (126.80–127.56°) ligands were calculated using DFT. The bite-angle of the t -Bu-xantphos ligands is larger due to the increased steric bulk of the tert -butyl substituents. The electronic properties of the t -Bu-xantphos ligandswere also investigated by synthesis of their phosphine selenides. The values of ¹J PSe (689.1–698.5Hz) indicate that the t -Bu-xantphos ligands have a higher basicity than Ph-xantphos between PPh₂Me and PMe₃. The silver complexes, [Ag(t -Bu-xantphos)Cl] and [Ag(t -Bu-xantphos)]BF₄ were synthesised with the t -Bu-xantphos ligands. In contrast to systems with phenyl phosphines, all species were monomeric. [Rh(t -Bu-xantphos)Cl] complexes were synthesised, which reacted with H₂, forming [Rh(t -Bu-xantphos-ĸP,O,P ’)Cl(H)₂] complexes, and with CO, forming [Rh(t -Bu-xantphos)(CO)₂Cl] complexes. The [Rh(t -Bu-xantphos)Cl] species are air-sensitive readily forming [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)] complexes. The crystal structure of [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)], contained 15% of the dioxygen sites replaced with an oxo ligand. This is the first crystallographic evidence of a rhodium(III) oxo complex, and only the third rhodium oxo species reported. The coordination chemistry of the ligands with platinum(0) and palladium(0) showed some differences. [Pt(t -Bu-xantphos)(C₂H₄)] complexes were synthesised for all three ligands. However, reaction with [Pt(nb)₃] produced a mixture of [Pt(t -Bu-xantphos)] and [Pt(t -Bu-xantphos)(nb)] for t -Bu-sixantphos and t -Buthixantphos. Although few examples of isolable [Pt(PP)] complexes with diphosphines have been reported [Pt(t -Bu-thixantphos)] was isolated by removal of the norbornene. t -Bu-Xantphos formed small amounts of [Pt(t -Bu-xantphos)] initially, which progressed to [Pt(t -Bu-xantphos)H]X. The analogous reactions with [Pd(nb)₃] gave [Pd(t -Bu-xantphos)] and [Pd(t -Bu-xantphos)(nb)] complexes in all cases. [Pt(t -Bu-thixantphos)(C₂H₄)] and [M(t -Bu-thixantphos)] (M = Pd, Pt) react with oxygen forming [Pt(t -Bu-thixantphos)(ƞ²-O₂)], which reacts with CO to give [Pt(t -Bu-thixantphos-H-ĸ-C,P,P ’)OH] through a series of intermediates. [M(t -Bu-xantphos)Cl₂] (M = Pd, Pt) complexes were synthesised, showing exclusive trans coordination of the diphosphine ligands. The X-ray crystal structure of [Pt(t -Bu-thixantphos)Cl₂] has a bite-angle of 151.722(15)°. This is the first [PtCl₂(PP)] complex with a bite-angle between 114 and 171°. In polar solvents a chloride ligand dissociates from the [Pt(t -Bu-xantphos)Cl₂] complexes producing [Pt(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺. The analogous [Pd(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺ complexes were formed by reaction of the dichlorides complexes with NH₄PF₆. The [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ pincer complexes were the only product from reaction with [Pt(C₆H₁₀)ClMe], with the stronger trans influence of the methyl ligand promoting loss of the chloride. The formation of the pincer complexes was further explored using DFT. The values of J PtC for the methyl carbons in the [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ complexes, and J RhH for the hydride trans to the oxygen atom in the [Rh(t -Buxantphos-ĸP,O,P ’)Cl(H)₂] complexes were largest for t -Bu-sixantphos, then t -Buthixantphos, then t -Bu-xantphos. The trans influence of the t -Bu-xantphos oxygen donor follows the trend t -Bu-sixantphos < t -Bu-thixantphos < t -Bu-xantphos.</p>

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In situ formation of ligand 2,2′-[(E)-diazene-1,2-diyldicarbonothioyl]diphenol and structural characterization of its binuclear rhodium(v) complex containing RhO2+

Cited by 4 publications

References 6 publications

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Thiohydrazide complexes of molybdenum and their relevance to reduction of dinitrogen to ammonia

Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

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