Activation and transfer of O2 to organic electrophiles by [RuH(dcpe)2]+

Martelletti, Arianna; Gramlich, Völker; Zürcher, F.; Mezzetti, Antonio

doi:10.1039/a808860h

Cited by 11 publications

(27 citation statements)

References 50 publications

(2 reference statements)

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“…This complex exhibited a low-frequency triplet hydride signal in THF- d 8 at δ −32.32 ( 2 J HP = 23 Hz). This chemical shift is more in line with the values reported for the all-phosphine analogues [Ru(P–P) 2 H] + (P–P = R 2 PCH 2 CH 2 PR 2 ; R = Cy, i Pr), rather than the all-carbene derivatives [Ru(NHC) 4 H] + (NHC = IMe 4 , IEt 2 Me 2 , I i Pr 2 Me 2 ), which appear at significantly lower frequency (ca. δ −41). , The mutual trans disposition of the two IMe 4 and two PPh 3 ligands found in the X-ray crystal structure of 11 (see further below) was supported by the presence of a high-frequency triplet 13 C{ 1 H} NMR signal with a cis - 31 P coupling of 14 Hz.…”

Section: Resultssupporting

confidence: 89%

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

et al. 2013

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Addition of IMe4 (1,3,4,5-tetramethylimidazol-2-ylidene) to Ru(PPh3)3HCl (in the presence of H2) or Ru(PPh3)4H2 gave the all-trans isomer of Ru(IMe4)2(PPh3)2H2 (1a), whereas 1,3-diethyl-4,5-dimethylimidazol-2-ylidene (IEt2Me2) reacted with Ru(PPh3)4H2 to form cis,cis,trans-Ru(IEt2Me2)2(PPh3)2H2 (2b). H/D exchange of 1a with C6D6 (elevated temperature) or D2 (room temperature) gave Ru(IMe4)2(PPh3)2HD (1a-HD) and Ru(IMe4)2(PPh3)2D2 (1a-D 2 ). CO reacted with 1a to give a mixture of Ru(IMe4)2(PPh3)(CO)H2 (3) and Ru(IMe4)2(CO)3 (4); 2b reacted in a similar manner, although more slowly, allowing isolation of the monocarbonyl species Ru(IEt2Me2)2(PPh3)(CO)H2 (5). Insertion of CO2 into one of the Ru–H bonds of 1a and 2b generated mixtures of major and minor isomers of the κ2-formate complexes Ru(IMe4)2(PPh3)(OCHO)H (7/8) and Ru(IEt2Me2)2(PPh3)(OCHO)H (9/10). The hydridic nature of 1a and 2b was apparent by their reactivity toward MeI, which gave [Ru(IMe4)2(PPh3)2H]I (11), Ru(IEt2Me2)2(PPh3)HI (12), [Ru(IEt2Me2)2(PPh3)2H]I (13), and Ru(IEt2Me2)(PPh3)2HI (14). Complexes 1a, 2b, 5, 9, 11, 13, and 14 were structurally characterized.

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Section: Resultssupporting

confidence: 89%

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

et al. 2013

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“…“Pretime” is the pretreatment time during which the sample is exposed to H 2 and not CO 2 . b Reference 46. c Average of five crystallographically determined angles from refs −49. d Reference 48. e Reference 50. f Average of three angles from refs and .…”

Section: Resultsmentioning

confidence: 99%

In Situ Formation of Ruthenium Catalysts for the Homogeneous Hydrogenation of Carbon Dioxide

et al. 2002

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A total of 44 different phosphines were tested, in combination with [RuCl(2)(C(6)H(6))](2) and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of CO(2) to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe(3), PPhMe(2), dppm, dppe, and cis- and trans-Ph(2)PCH=CHPPh(2). The in situ catalysts prepared from [RuCl(2)(C(6)H(6))](2) and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O(2)CMe)(PMe(3))(4). There was no correlation between the basicity of monophosphines (PR(3)) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ (31)P NMR spectroscopy showed that trans-Ru(H)(2)(dppm)(2), trans-RuCl(2)(dppm)(2), trans-RuHCl(dppm)(2), cis-Ru(H)(O(2)CH)(dppm)(2), and cis-Ru(O(2)CH)(2)(dppm)(2) are produced as the major metal-containing species in reactions of dppm with [RuCl(2)(C(6)H(6))](2) under catalytic conditions at 50 degrees C.

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“…The 31 P NMR spectra of 4a − c consist of one sharp singlet in the range δ +10 to −10, consistent with rapid internal reorientation rendering all P atoms equivalent. In contrast, the 31 P NMR spectra of the related complexes [MH(η 2 -O 2 )(P−P) 2 ] (M = Ru, Os) show broad signals at room temperature, possibly due to the hindered propeller-like rotation of the η 2 -O 2 ligand. ,, …”

Section: Resultsmentioning

confidence: 96%

Oxo Complexes of Osmium(IV) Formed via Dioxygen Activation. X-ray Structures of [OsX(dcpe)₂]PF₆ (X = Cl, Br), [OsCl(η²-O₂)(dcpe)₂]BPh₄, and [OsCl(O)(dcpe)₂]BPh₄ (dcpe = 1,2-Bis(dicyclohexylphosphino)ethane)

et al. 2000

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Dioxygen addition to the 16-electron complexes [OsX(P-P)2]+ (3) gives the dioxygen adducts [OsCl(eta 2-O2)(P-P)2]+ (3), which in turn react with HCl gas to give the novel osmium(IV) oxo complexes trans-[OsX(O)(P-P)2]+ (5) (X = Cl, Br; P-P = 1,2-bis(dicyclohexylphosphino)ethane (dcpe), 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene (Me-duphos)). The complexes [OsX(dcpe)2]+ (X = Cl, Br) (3) are studied by X-ray crystallography and are shown to have a "Y-shaped" coordination geometry in the equatorial plane. The X-ray structural analysis of [OsCl(eta 2-O2)(dcpe)2]+ (4a) reveals an exceptionally short O-O bond (1.315(5) A). trans-[OsCl(O)(dcpe)2]+ (5a), the first oxo complex of osmium(IV) investigated crystallographically, exhibits a long Os-O distance of 1.834(3) A. The reactivity of 4 and 5 as oxidants is described. The dioxygen complex 4a transfers one oxygen atom to PPh3 (to give Ph3PO) or oxidizes iodide ions to triiodide ions in the presence of anhydrous HCl. In both reactions, the corresponding oxo species 5a is quantitatively formed as the only metal-containing product. Oxo complexes 5 are surprisingly stable and unreactive toward standard reducing agents such as phosphines.

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Activation and transfer of O2 to organic electrophiles by [RuH(dcpe)2]+

Cited by 11 publications

References 50 publications

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

In Situ Formation of Ruthenium Catalysts for the Homogeneous Hydrogenation of Carbon Dioxide

Oxo Complexes of Osmium(IV) Formed via Dioxygen Activation. X-ray Structures of [OsX(dcpe)₂]PF₆ (X = Cl, Br), [OsCl(η²-O₂)(dcpe)₂]BPh₄, and [OsCl(O)(dcpe)₂]BPh₄ (dcpe = 1,2-Bis(dicyclohexylphosphino)ethane)

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Activation and transfer of O2 to organic electrophiles by [RuH(dcpe)2]+

Cited by 11 publications

References 50 publications

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)2(PPh3)2H2(NHC = N-Heterocyclic Carbene)

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)2(PPh3)2H2(NHC = N-Heterocyclic Carbene)

In Situ Formation of Ruthenium Catalysts for the Homogeneous Hydrogenation of Carbon Dioxide

Oxo Complexes of Osmium(IV) Formed via Dioxygen Activation. X-ray Structures of [OsX(dcpe)2]PF6 (X = Cl, Br), [OsCl(η2-O2)(dcpe)2]BPh4, and [OsCl(O)(dcpe)2]BPh4 (dcpe = 1,2-Bis(dicyclohexylphosphino)ethane)

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Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

Synthesis and Small Molecule Reactivity oftrans-Dihydride Isomers of Ru(NHC)₂(PPh₃)₂H₂(NHC = N-Heterocyclic Carbene)

Oxo Complexes of Osmium(IV) Formed via Dioxygen Activation. X-ray Structures of [OsX(dcpe)₂]PF₆ (X = Cl, Br), [OsCl(η²-O₂)(dcpe)₂]BPh₄, and [OsCl(O)(dcpe)₂]BPh₄ (dcpe = 1,2-Bis(dicyclohexylphosphino)ethane)