Unprecedented dimethyl sulfoxide conformational equilibria and kinetics on [Ir(Me2SO)3(η-C5Me5)][PF 6]2

Cusanelli, Antonio; Frey, Urban; Merbach, André E.

doi:10.1039/a606982g

Cited by 10 publications

(11 citation statements)

References 3 publications

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“…Including the data available for the Cr, W and Ru homologues, the same trend is observed in group 6 ( 6 ] 3+ aqua ions [48,49], where the increase in bond strength leads even to a change in the water exchange mechanism from I d to I a [50]. The electrostatic interaction is influencing the metal water bond strength which is also clearly visible in the increased activation enthalpies, H ‡ , for the water exchange (Table 3) and certainly also contributes to the slower water exchange rates on fac-[(CO) 2 13 CO in a 10 mm NMR sapphire tube [52,53]. The CO exchange was monitored by 99 Tc NMR (Fig.…”

Section: Water Exchange On Fac-[(co) 3 M(h 2 O)] + -Comparisonsmentioning

confidence: 94%

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

Helm

2008

Coordination Chemistry Reviews

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Section: Water Exchange On Fac-[(co) 3 M(h 2 O)] + -Comparisonsmentioning

confidence: 94%

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

Helm

2008

Coordination Chemistry Reviews

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“…Similar behavior to that observed for complex 3 was recently observed in the case of the Ir III complex [Cp*Ir(DM-SO) 3 ][PF 6 ] 2 . [9] In contrast to the Ir III complex, rapid exchange between bound and free DMSO was not observed for 3, even when the temperature of a CD 2 Cl 2 solution of 3 in the presence of free DMSO was lowered. The structures of complexes 1 ± 3 are supported by elemental analyses, and in the case of compounds 1 and 2, single crystals suitable for X-ray diffraction studies were grown directly from more dilute reaction mixtures.…”

mentioning

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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“…At low rhodium cluster concentration (5 [17 -23] A limitation of our earlier design of HPNMR cell was that agitation of the sample, to ensure good gas dissolution, was not incorporated into the design for reasons of mechanical complexity. [24,25] As a result, the rates of the cleavage reactions were determined by very slow gas diffusion across the interface into, or out of, solution reactions taking up to 48 h to reach equilibrium. In contrast, efficient gas mixing is achieved in the HPNMR bubble column allowing equilibrium to be rapidly established, albeit at the expense of a reduced maximum working pressure (ca 250 bar in the bubble column vs ca 1 kbar for the earlier design).…”

Section: S101mentioning

confidence: 99%

The reaction of mixtures of [Rh4(CO)12] and triphenylphosphite with carbon monoxide or syngas as studied by high-resolution, high-pressure NMR spectroscopy

et al. 2008

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The fragmentation and redistribution reactions of [Rh4(CO)12-x{P(OPh)3}x] (x = 1-4) with carbon monoxide have been studied using high-resolution, high-pressure NMR spectroscopy. Under the conditions of efficient gas mixing in a high-pressure NMR bubble column, [Rh4(CO)9{P(OPh)3}3] fragments to give mainly [Rh2(CO)6{P(OPh)3}2]; [Rh4(CO)11{P(OPh)3}] is also observed,implying redistribution of the phosphite ligand and/or recombination of the dimers to tetrameric clusters. Fragmentation of[Rh4(CO)10{P(OPh)3}2] is found to be pressure-dependent giving predominantly [Rh2(CO)6{P(OPh)3}2] at low CO pressure (1-40 bar), and increasing amounts of [Rh2(CO)7{P(OPh)3}] at higher (40-80 bar) pressure. Using Syngas (CO : H2 (1 : 1)) instead of CO in the above fragmentations, homolytic addition of H2 to the dimer [Rh2(CO)6{P(OPh)3}2] to give [RhH(CO)3{P(OPh3}] and [RhH(CO)2{P(OPh)3}2] is observed. The distribution of tetrameric species obtained is similar to that obtained under the same partial pressure of CO. On depressurisation/out-gassing of the sample, the original mixture of tetrameric clusters is obtained.

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Unprecedented dimethyl sulfoxide conformational equilibria and kinetics on [Ir(Me2SO)3(η-C5Me5)][PF 6]2

Cited by 10 publications

References 3 publications

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

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

The reaction of mixtures of [Rh4(CO)12] and triphenylphosphite with carbon monoxide or syngas as studied by high-resolution, high-pressure NMR spectroscopy

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Unprecedented dimethyl sulfoxide conformational equilibria and kinetics on [Ir(Me2SO)3(η-C5Me5)][PF 6]2

Cited by 10 publications

References 3 publications

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M=Mn, Tc, Re)

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

The reaction of mixtures of [Rh4(CO)12] and triphenylphosphite with carbon monoxide or syngas as studied by high-resolution, high-pressure NMR spectroscopy

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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)