Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

James, Brian R.; Morris, Robert H.; Reimer, Kenneth J.

doi:10.1139/v77-322

Cited by 39 publications

(9 citation statements)

References 20 publications

(30 reference statements)

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“…Cleavage of the chloride bridge in [RhCl(diene)], complexes by a Lewis base L, including monodentate phosphines, can yield both RhCl(diene)L and Rh(diene)L,'Clspecies, depending on the amount of L used and the polarity of the solvent used (23). Reaction of the diene dimer with 2 mol of a chelating diphosphine is assumed to yield RhCl(diphosphine) (solvent) or Rh(diene)(diphosphine)+, de starting fi-om rhodiurn trichloride (29).…”

Section: Resultsmentioning

confidence: 99%

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

James¹,

Mahajan²

1979

Can. J. Chem.

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Rhodium(1)-bis(ditertiaryphosphine) complexes of the general formula R~( P^P ) , ~1(PnP = Ph,P(CH,),,PPh,, n = 1-4, and (+)-diop (diop = 2,3-0-isopropylidene 2,3-dihydroxy-1,4-bis(dipheny1phosphino)butane) have been prepared by treating [Rh(cyclooctene),CI], with the appropriate ditertiaryphosphine. The n = 1 and n = 4 and diop species are five-coordinate in the solid state and in non-polar solvents, while the n = 2 and 3 species contain ionic chloride. The cationic complexes R~( P P ) , + x -were prepared from the R~(P^P),CI species by adding AgX (X = SbF,, PF,, BF,). Reaction of the chloro coniplexes with borohydride has yielded the hydrides, HRh(PnP),, for the n = 2 and 3 diphosphines, and for (+)-diop. 'H and 31P nmr, as well as visible rpectral data, are presented: a solventdependent deshielding of ort/~o protons of the phenyl groups is observed in some of the cornplexes, and the ligand CH2 protons are coupled to the rhodium in the Rh(Ph,PCH,PPh2),+ cation; the P atom in this bis(dipheny1phosphino) ligand shows an usual high field shift on coordination to rhodium.Preliminary kinetic data for catalytic hydrogenation of methylenesuccinic acid show that the cationic and hydrido colnplexes are more active than the corresponding chloro coniplexes, and that activity generally increases with increasing chain length of the diphosphine. avec la phosphineditertiaire appropriee. Les especes ou n = 1, IZ = 4 et diop sont pentacoordonnees a I'ttat solide et dans des solvants non-polaires alors que les especes ou 11 = 2 et 12 = 3 contiennent du chlorure ionique. On a prepare les complexes cationiques R~(P-P),+x-a partir des especes Rh(PAP),C1 auxquelles on a ajoute du AgX (X = SbF,, PF,, BF,). La reaction des complexes chlores avec le borohydrure conduit aux hydrures, HR~(P-P),, pour les diphosphines ou tr = 2 et 3 et pour le (+)-diop. On presente les spectres rnin 'H et 3'P de meme que les spectres dans le visible: dans quelques-un des complexes, on observe un deblindage des protons ortho des groupes phenyles qui depend du solvent et, dans le cation Rh(Ph,PCH,PPh,),-, les protons du CH, du ligand sont couples au rhodium: l'aton~e de P de ce ligand bis(dipheny1phosphino) subit un deplacement usuel vers les hauts champs par coordination avec le rhodium.Des donnees cinetiques preliminaires concernant Ishydrogenation catalytique de I'acide methylenesuccinique montrent que les con~plexes cationiques et hybrido sont plus actifs que Ics complexes chloro correspondants et que gentralement I'activiti augmente avec une augmentation de la longueur de la chaine de la diphosphine.[Traduit par le journal]

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Section: Resultsmentioning

confidence: 99%

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

James¹,

Mahajan²

1979

Can. J. Chem.

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“…[23,24] Based on IR spectroscopic data and their lability in solution, these com- plexes were believed to have O-bound DMSO ligands. To ascertain the exact structure of these compounds, we synthesized complex [Rh(cod)(DMSO) 2 ]BF 4 (11) and characterized it by X-ray crystallogrphy.…”

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confidence: 99%

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Dorta

Rozenberg

Shimon

et al. 2003

Chemistry A European J

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Novel neutral and cationic Rh(I) and Ir(I) complexes that contain only DMSO molecules as dative ligands with S-, O-, and bridging S,O-binding modes were isolated and characterized. The neutral derivatives [RhCl(DMSO)(3)] (1) and [IrCl(DMSO)(3)] (2) were synthesized from the dimeric precursors [M(2)Cl(2)(coe)(4)] (M=Rh, Ir; COE=cyclooctene). The dimeric Ir(I) compound [Ir(2)Cl(2)(DMSO)(4)] (3) was obtained from 2. The first example of a square-planar complex with a bidentate S,O-bridging DMSO ligand, [(coe)(DMSO)Rh(micro-Cl)(micro-DMSO)RhCl(DMSO)] (4), was obtained by treating [Rh(2)Cl(2)(coe)(4)] with three equivalents of DMSO. The mixed DMSO-olefin complex [IrCl(cod)(DMSO)] (5, COD=cyclooctadiene) was generated from [Ir(2)Cl(2)(cod)(2)]. Substitution reactions of these neutral systems afforded the complexes [RhCl(py)(DMSO)(2)] (6), [IrCl(py)(DMSO)(2)] (7), [IrCl(iPr(3)P)(DMSO)(2)] (8), [RhCl(dmbpy)(DMSO)] (9, dmbpy=4,4'-dimethyl-2,2'-bipyridine), and [IrCl(dmbpy)(DMSO)] (10). The cationic O-bound complex [Rh(cod)(DMSO)(2)]BF(4) (11) was synthesized from [Rh(cod)(2)]BF(4). Treatment of the cationic complexes [M(coe)(2)(O=CMe(2))(2)]PF(6) (M=Rh, Ir) with DMSO gave the mixed S- and O-bound DMSO complexes [M(DMSO)(2)(DMSO)(2)]PF(6) (Rh=12; Ir=in situ characterization). Substitution of the O-bound DMSO ligands with dmbpy or pyridine resulted in the isolation of [Rh(dmbpy)(DMSO)(2)]PF(6) (13) and [Ir(py)(2)(DMSO)(2)]PF(6) (14). Oxidative addition of hydrogen to [IrCl(DMSO)(3)] (2) gave the kinetic product fac-[Ir(H)(2)Cl(DMSO)(3)] (15) which was then easily converted to the more thermodynamically stable product mer-[Ir(H)(2)Cl(DMSO)(3)] (16). Oxidative addition of water to both neutral and cationic Ir(I) DMSO complexes gave the corresponding hydrido-hydroxo addition products syn-[(DMSO)(2)HIr(micro-OH)(2)(micro-Cl)IrH(DMSO)(2)][IrCl(2)(DMSO)(2)] (17) and anti-[(DMSO)(2)(DMSO)HIr(micro-OH)(2)IrH(DMSO)(2)(DMSO)][PF(6)](2) (18). The cationic [Ir(DMSO)(2)(DMSO)(2)]PF(6) complex (formed in situ from [Ir(coe)(2)(O=CMe(2))(2)]PF(6)) also reacts with methanol to give the hydrido-alkoxo complex syn-[(DMSO)(2)HIr(micro-OCH(3))(3)IrH(DMSO)(2)]PF(6) (19). Complexes 1, 2, 4, 5, 11, 12, 14, 17, 18, and 19 were characterized by crystallography.

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“…Ddios will again be a mixture of diastereomers. 1 This complex was prepared by (a), the addition of dios to the 'blue solution' formed on refluxing RuCl,.3H20 in methanol under 1 atm Hz (11,12); and by (b), sulfoxide exchange with cis-RuCl,(dmso), (13) in methanol. Compound 1, which gives the correct elemental analysis, is a yellow solid, insoluble in acetone, slightly soluble in alcohols, and more soluble in water and NN-dimethylacetamide (dma), in which it is non-ionic.…”

Section: Sulfoxide Ligandsmentioning

confidence: 99%

“…Results and Discussion Our continuing interest in asymmetric homogeneous hydrogenation, especially using ruthenium(I1) and rhodium(1) catalysts containing chiral phosphine and sulfoxide ligands (1)(2)(3), has led us to the development of three new chelating chiral sulfoxide ligands : (2R,3R)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(methy1 su1finyl)-butane monohydrate, the corresponding bis-(benzyl sulfinyl) derivative, and (2R,3R)-2,3-dihydroxy-l,Cbis(methyl suliinyl)butane. We have named these ligands dios, bdios, and ddios, respectively, since they are patterned after the chelating phosphine derivative diop, developed by Kagan and Dang (4).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Catalytic asymmetric hydrogenation using ruthenium(II) complexes with chelating chiral sulfoxide ligands

James¹,

McMillan²

1977

Can. J. Chem.

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A chelating sulfoxide ligand, (2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(methyl sulfinyl)butane monohydrate, or 'dios', containing chiral carbons has been synthesized. A corresponding bis(benzyl sulfinyl) compound, 'bdios', and an acetal-cleaved derivative, 'ddios', are also reported. Ruthenium(II) neutral complexes have been made containing such ligands, which can bind via oxygen or sulphur; the complexes are active homogeneous catalysts for hydrogenation of prochiral olefinic acid substrates; optical purities of up to 25% were attained.

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Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

Cited by 39 publications

References 20 publications

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Catalytic asymmetric hydrogenation using ruthenium(II) complexes with chelating chiral sulfoxide ligands

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Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

Cited by 39 publications

References 20 publications

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

Bis(ditertiaryphosphine) complexes of rhodium(I). Synthesis, spectroscopy, and activity for catalytic hydrogenation

Dimethylsulfoxide as a Ligand for RhI and IrI Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH3)

Catalytic asymmetric hydrogenation using ruthenium(II) complexes with chelating chiral sulfoxide ligands

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Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)