Mono-, bis-, and tris(phosphine) derivatives of .mu.3-sulfido hydrido complexes of rhodium and iridium. Syntheses and x-ray crystal structures of 50-electron Rh3(H)(.mu.3-S)2(COD)2(PMe3)3 and Ir3(H)(.mu.3-S)2(COD)3(PMe3) and 48-electron Ir3(H)(.mu.3-S)2(COD)2(tert-Bu2PH)2 (COD = 1,5-cyclooctadiene)

Bright, Theresa A.; Jones, Richard A.; Koschmieder, Stefan U.; Nunn, Christine M.

doi:10.1021/ic00294a028

Cited by 22 publications

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“…Nevertheless, the formation of the hydride clusters [M 3 (μ 3 -S) 2 (μ-H)(cod) 3 ] (M = Rh, Ir) is minimized by using rhodium and iridium dinuclear compounds as starting materials. Thus, reaction of i Pr 2 C(SH) 2 with [Rh(μ-OH)(cod)] 2 or [Ir(μ-OMe)(cod)] 2 afforded the compounds [Rh 2 (μ-S 2 C i Pr 2 )(cod) 2 ] ( 2 ) and [Ir 2 (μ-S 2 C i Pr 2 )(cod) 2 ] ( 4 ), which were isolated as orange and purple microcrystalline solids in 76% yield after chromatography purification to remove the hydride clusters (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…The diolefin complexes [M 2 (μ-S 2 CR 2 )(cod) 2 ] (M = Rh, Ir) are accessible from the dinuclear complexes [M(μ-OH)(cod)] 2 and [M(μ-OMe)(cod)] 2 , or the mononuclear [M(acac)(cod)], sometimes in the presence of an external base. The dinuclear complexes are generally obtained in high yield although, in the case of i Pr 2 C(SH) 2 , the syntheses are complicated by the formation of the trinuclear hydride clusters [M 3 (μ 3 -S) 2 (μ-H)(cod) 3 ] which can be easily separated by chromatography. The formation of the sulfido clusters resulted from the SH 2 (g) produced in the decomposition of i Pr 2 C(SH) 2 as has been evidenced by the detection of i Pr 2 CS by GC/MS.…”

Section: Discussionmentioning

confidence: 99%

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Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

et al. 2008

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The reaction of gem-dithiol compounds R 2C(SH) 2 (R = Bn (benzyl), (i) Pr; R 2 = -(CH 2) 4-) with dinuclear rhodium or iridium complexes containing basic ligands such as [M(mu-OH)(cod)] 2 and [M(mu-OMe)(cod)] 2, or the mononuclear [M(acac)(cod)] (M = Rh, Ir, cod = 1,5-cyclooctadiene) in the presence of a external base, afforded the dinuclear complexes [M 2(mu-S 2CR 2)(cod) 2] ( 1- 4). The monodeprotonation of 1,1-dimercaptocyclopentane gave the mononuclear complex [Rh(HS 2Cptn)(cod)] ( 5) that is a precursor for the dinuclear compound [Rh 2(mu-S 2Cptn)(cod) 2] ( 6). Carbonylation of the diolefin compounds gave the complexes [Rh 2(mu-S 2CR 2)(CO) 4] ( 7- 9), which reacted with P-donor ligands to stereoselectively produce the trans isomer of the disubstituted complexes [Rh 2(mu-S 2CR 2)(CO) 2(PR' 3) 2] (R' = Ph, Cy (cyclohexyl)) ( 10- 13) and [Rh 2(mu-S 2CBn 2)(CO) 2{P(OR') 3} 2] (R' = Me, Ph) ( 14- 15). The substitution process in [Rh 2(mu-S 2CBn 2)(CO) 4] ( 7) by P(OMe) 3 has been studied by spectroscopic means and the full series of substituted complexes [Rh 2(mu-S 2CBn 2)(CO) 4- n {P(OR) 3} n ] ( n = 1, 4) has been identified in solution. The cis complex [Rh 2(mu-S 2CBn 2)(CO) 2(mu-dppb)] ( 16) was obtained by reaction of 7 with the diphosphine dppb (1,4-bis(diphenylphosphino)butane). The molecular structures of the diolefinic dinuclear complexes [Rh 2(mu-S 2CR 2)(cod) 2] (R = Bn ( 1), (i) Pr ( 2); R 2 = -(CH 2) 4- ( 6)) and that of the cis complex 16 have been studied by X-ray diffraction.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

et al. 2008

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“…Nevertheless, a straightforward and clean synthesis of [Cp tt 2 Zr(μ 3 -S) 2 {Rh(cod)} 2 ] ( 3 ) consisted of the reaction of [Cp tt 2 Zr(SH) 2 ] with [{Rh(μ-OH)(cod)} 2 ] in methanol at room temperature. However, the identical reaction of [Cp tt 2 Zr(SH) 2 ] with 1 molar equiv of [{Ir(μ-OH)(cod)} 2 ] in tetrahydrofuran/methanol gave the triiridium hydride complex [Ir 3 (μ-S) 2 (μ-H)(cod) 3 ], which was isolated in 90% yield. On the other hand, the reaction of [Cp tt 2 Zr(SH) 2 ] with 2 molar equiv of [Ir(acac)(cod)] in diethyl ether afforded the new complex [Cp tt (acac)Zr(μ 3 -S) 2 {Ir(cod)} 2 ] ( 5 ) with [Ir 3 (μ-S) 2 (μ-H)(cod) 3 ] as an impurity; complex 5 could be isolated pure as a dark blue solid by recrystallization.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes

et al. 2003

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SummaryReactions of the zirconium-sulfide metallocene anion [Cp tt 2 ZrS 2 ] 2-(Cp tt = η 5 -1,3-di-tertbutylcyclopentadienyl) with [{M(µ-Cl) with one molar-equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cp tt 2 Zr(µ 3 -S) 2 {M(CO)} 2 (µ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide.Monodentate phosphites, P(OMe) 3 and P(OPh) 3, react with 6 to give mixtures of the transoid and cisoid isomers [Cp tt 2 Zr(µ 3 -S) 2 {Rh(CO)(P(OR) 3 )} 2 ], which also exhibit a restricted rotation of the Cp tt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe) 3 , P(OPh) 3, and 40 PPh 3 , is a precursor of catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature.

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“…A similar protocol using Cp 2 Ti(SH) 2 and [{Ir(μ-OMe)(cod)} 2 ] is not suitable for the synthesis of the analogous Ti−Ir complex [CpTi(μ 3 -S) 3 {Ir(cod)} 3 ]. This reaction follows an alternative pathway resulting in the formation of the known cluster [Ir 3 (μ 3 -S) 2 (μ-H)(cod) 3 ] in high yield. As the hydridoiridium cluster can be obtained from [{Ir(μ-Cl)(cod)} 2 ] and NaHS or H 2 S, the titanium complex acts as a source of hydrosulfido ligands for iridium, one of which produces the oxidative-addition of the S−H bond leading to the hydrido ligand.…”

Section: Resultsmentioning

confidence: 99%

Sulfido-Bridged Tetranuclear Titanium−Iridium Complexes with an Unconventional Tetrahedral Iridium Center

et al. 1999

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A general route to the complexes [CpTi(μ3-S)3M3(diolefin)3] (M = Rh, diolefin = cod, nbd, tfbb; M = Ir, diolefin = cod) consists of the reactions of the anion [Cp2Ti2(μ-S)2(S)2]2-, obtained by mono-deprotonation of Cp2Ti(SH)2 with butyllithium in THF, with the appropriate complexes [{M(μ-Cl)(diolefin)}2]. Replacement of the diolefin by carbon monoxide in [CpTi(μ3-S)3M3(diolefin)3] gives the carbonyl derivatives [CpTi(μ3-S)3M3(CO)6]. Further reactions of the carbonyliridium complex with tertiary phosphine and phosphite ligands produce the 62-e valence clusters [CpTi(μ3-S)3Ir3(μ-CO)(CO)3(PR3)3] (PR3 = PPh3, PMe3, P(OMe)3, PMePh2). Remarkable features in the structure of these compounds, as found for [CpTi(μ3-S)3Ir3(μ-CO)(CO)3{P(OMe)3}] by X-ray diffraction studies, are a distorted tetrahedral metal framework with short Ir−Ir distances and a tetrahedral coordination of the iridium atom closest to the titanium. A delocalized bonding scheme can be proposed for the iridium triangle and, at least, an interaction between the tetrahedral iridium and the titanium atom. The complexes [CpTi(μ3-S)3Ir3(μ-CO)(CO)3(PR3)3] quickly exchange all their carbonyl ligands with 13CO under normal conditions to give the labeled complexes. Indeed, an equilibrium between the compounds [CpTi(μ3-S)3Ir3(μ-13CO)(13CO)3(PR3)3] and [CpTi(μ3-S)3Ir3(μ-13CO)(13CO)4(PR3)2] and free phosphine exists under an atmosphere of 13CO. In addition, these compounds are fluxional, since they exhibit a single carbonyl resonance in the low-temperature 13C{1H} NMR spectrum, probably due to very fast carbonyl scrambling. Furthermore, the reaction of [CpTi(μ3-S)3Ir3(μ-CO)(CO)3(PPh3)3] with HBF4 gives the unsymmetric and nonfluxional hydride of formula [CpTi(μ3-S)3Ir3(μ-CO)(H)(CO)3(PPh3)3]BF4.

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Mono-, bis-, and tris(phosphine) derivatives of .mu.3-sulfido hydrido complexes of rhodium and iridium. Syntheses and x-ray crystal structures of 50-electron Rh3(H)(.mu.3-S)2(COD)2(PMe3)3 and Ir3(H)(.mu.3-S)2(COD)3(PMe3) and 48-electron Ir3(H)(.mu.3-S)2(COD)2(tert-Bu2PH)2 (COD = 1,5-cyclooctadiene)

Cited by 22 publications

References 0 publications

Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes

Sulfido-Bridged Tetranuclear Titanium−Iridium Complexes with an Unconventional Tetrahedral Iridium Center

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Mono-, bis-, and tris(phosphine) derivatives of .mu.3-sulfido hydrido complexes of rhodium and iridium. Syntheses and x-ray crystal structures of 50-electron Rh3(H)(.mu.3-S)2(COD)2(PMe3)3 and Ir3(H)(.mu.3-S)2(COD)3(PMe3) and 48-electron Ir3(H)(.mu.3-S)2(COD)2(tert-Bu2PH)2 (COD = 1,5-cyclooctadiene)

Cited by 22 publications

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Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

Synthesis, Structural Characterization, and Ligand Replacement Reactions ofgem-Dithiolato-Bridged Rhodium and Iridium Complexes

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM2(M = Rh, Ir) Early−Late Heterobimetallic Complexes

Sulfido-Bridged Tetranuclear Titanium−Iridium Complexes with an Unconventional Tetrahedral Iridium Center

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Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes