17. Some η
            <sup>5</sup>
            ‐Cyclopentadienylruthenium(II) Complexes Containing Triphenylphosphine

Bruce, Michael I.; Hameister, C.; Swincer, A. Geoffrey; Wallis, Robert C.; Ittel, Steven D.

doi:10.1002/9780470132524.ch17

Cited by 172 publications

(65 citation statements)

References 16 publications

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“…We have been able to present a clearer picture of the mechanistic aspects of the reaction, and more interestingly, we have demonstrated that the carbonyl complexes resulting from aldehyde decarbonylation, which is usually regarded as the cause of catalyst deactivation, are also active for the alkylation reactions. [14] CpRu-A C H T U N G T R E N N U N G (PPh 3 ) 2 Cl (M2), [15] CpRuA C H T U N G T R E N N U N G (dppm)Cl (M3), [16] TpRuA C H T U N G T R E N N U N G (PPh 3 ) 2 Cl (M4), [17] [18] cis-[Ru(6,6'- [19] and TpRuA C H T U N G T R E N N U N G (PPh 3 )(CO)Ph (M8) [10] were prepared according to literature methods.…”

Section: Discussionmentioning

confidence: 99%

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

et al. 2008

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Cyclopentadienyl (Cp), hydrotris(pyrazolyl)borato (Tp), and bipyridine ruthenium complexes were found to be active catalysts for the b-alkylation of secondary alcohols with primary alcohols. Mechanistic aspects of the Cp and Tp complexes-catalyzed reactions were investigated; the crucial hydrido complexes were identified. Carbonyl complexes resulting from aldehyde decarbonylation were formed in some cases, and surprisingly, they were also found to be active for the catalytic processes.

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Section: Discussionmentioning

confidence: 99%

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

et al. 2008

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“…[34] Hydrated ruthenium(III) chloride, hydrated rhodium/iridium(III) chloride, dicyclopentadiene pentamethylcyclopentadiene, α-phellandrene, hexamethylbenzene, 2-(2-diphenylphosphanylethyl)pyridine (all Sigma-Aldrich) were used as received without further purifications. [35][36][37] General Methods: Elemental analyses for C, H, and N on the complexes were performed with an Exeter Analytical Inc. Model CE-440 elemental analyzer. IR and far-IR in KBr disk form were recorded with a Varian 3300 FTIR spectrophotometer, and electronic absorption spectra were recorded with a Shimadzu UV-1700 spectrophotometer.…”

Section: Methodsmentioning

confidence: 99%

Synthetic, Spectral, Structural, and Catalytic Aspects of Some Piano‐Stool Complexes Containing 2‐(2‐Diphenylphosphanylethyl)pyridine

et al. 2010

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Reactions of the complexes [(η5‐C5H5)Ru(PPh3)2Cl], [{(η6‐arene)Ru(μ‐Cl)Cl}2] (η6‐arene = C6H6, C10H14, and C6Me6) and [{(η5‐C5Me5)M(μ‐Cl)Cl}2] (M = Rh, Ir) with 2‐(2‐diphenylphosphanylethyl)pyridine (PPh2Etpy) were investigated. Neutral κ1‐P‐bonded complexes [(η5‐C5H5)Ru(κ1‐P‐PPh2EtPy)(PPh3)Cl] (1) and [(η6‐arene)Ru(κ1‐P‐PPh2EtPy)Cl2] [arene = C6H6, (2). C10H14, (3), and C6Me6, (4)] were isolated from the reactions of [(η5‐C5H5)Ru(PPh3)2Cl] and [{(η6‐arene)Ru(μ‐Cl)Cl}2] with PPh2EtPy. Treatment of 1–4 with NH4BF4/NH4PF6 in methanol allows the synthesis of cationic κ2‐P,N‐chelated complexes [(η5‐C5H5)Ru(κ2‐P,N‐PPh2EtPy)(PPh3)]+ (5) and [(η6‐arene)Ru(κ2‐P‐N‐PPh2EtPy)Cl]+ [arene = C6H6, (6), C6H14, (7), and C6Me6 (8)]. On the other hand, the dimers [{(η5‐C5Me5)M(μ‐Cl)Cl}2] (M = Rh or Ir) reacted with PPh2EtPy in methanol to afford cationic κ2‐P,N‐chelated complexes [(η5‐C5Me5)M(κ2‐P‐N‐PPh2EtPy)Cl]+ [M = Rh, (9); Ir, (10)]. Complex 10 reacted with an excess amount of sodium azide or sodium chloride to afford the complexes [(η5‐C5Me5)Ir(κ1‐P‐PPh2EtPy)X2] (X = N3– 11; Cl–, 12), establishing the hemilabile nature of the coordinated PPh2EtPy. The complexes were characterized by elemental analyses and various physicochemical techniques. The molecular structures of 1, 5, 6, 9, and 10 were determined crystallographically, and the catalytic potentials of 1–10 were evaluated towards transfer‐hydrogenation reactions under aqueous conditions.

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“…The easy-to-make, readily available and stable Ru II complex [CpRuClA C H T U N G T R E N N U N G (PPh 3 ) 2 ] (10) [17] gave the best results. Several attempts were made also using other Ru…”

Section: Resultsmentioning

confidence: 98%

“…All the other solvents were dried and degassed by an MB SPS solvent purification system. 1,4-Diethynylbenzene, [35] 1,3,5-triethynylbenzene, [36] [CpRuA C H T U N G T R E N N U N G (PPh 3 ) 2 Cl] [17] and [CpRuA C H T U N G T R E N N U N G (dppe)Cl] [37] were prepared from literature methods. Other reagents were obtained from commercial suppliers and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Cyclopentadienyl Ruthenium(II) Complexes with Bridging Alkynylphosphine Ligands: Synthesis and Electrochemical Studies

Credico

Biani

Gonsalvi

et al. 2009

Chemistry A European J

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The reaction of [CpRuCl(PPh(3))(2)] (Cp = cyclopentadienyl) and [CpRuCl(dppe)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)) with bis- and tris-phosphine ligands 1,4-(Ph(2)PC[triple bond]C)(2)C(6)H(4) (1) and 1,3,5-(Ph(2)PC[triple bond]C)(3)C(6)H(3) (2), prepared by Ni-catalysed cross-coupling reactions between terminal alkynes and diphenylchlorophosphine, has been investigated. Using metal-directed self-assembly methodologies, two linear bimetallic complexes, [{CpRuCl(PPh(3))}(2)(mu-dppab)] (3) and [{CpRu(dppe)}(2)(mu-dppab)](PF(6))(2) (4), and the mononuclear complex [CpRuCl(PPh(3))(eta(1)-dppab)] (6), which contains a "dangling arm" ligand, were prepared (dppab =1,4-bis[(diphenylphosphino)ethynyl]benzene). Moreover, by using the triphosphine 1,3,5-tris[(diphenylphosphino)ethynyl]benzene (tppab), the trimetallic [{CpRuCl(PPh(3))}(3)(mu(3)-tppab)] (5) species was synthesised, which is the first example of a chiral-at-ruthenium complex containing three different stereogenic centres. Besides these open-chain complexes, the neutral cyclic species [{CpRuCl(mu-dppab)}(2)] (7) was also obtained under different experimental conditions. The coordination chemistry of such systems towards supramolecular assemblies was tested by reaction of the bimetallic precursor 3 with additional equivalents of ligand 2. Two rigid macrocycles based on cis coordination of dppab to [CpRu(PPh(3))] were obtained, that is, the dinuclear complex [{CpRu(PPh(3))(mu-dppab)}(2)](PF(6))(2) (8) and the tetranuclear square [{CpRu(PPh(3))(mu-dppab)}(4)](PF(6))(4) (9). The solid-state structures of 7 and 8 have been determined by X-ray diffraction analysis and show a different arrangement of the two parallel dppab ligands. All compounds were characterised by various methods including ESIMS, electrochemistry and by X-band ESR spectroscopy in the case of the electrogenerated paramagnetic species.

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17. Some η ⁵ ‐Cyclopentadienylruthenium(II) Complexes Containing Triphenylphosphine

Cited by 172 publications

References 16 publications

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

Synthetic, Spectral, Structural, and Catalytic Aspects of Some Piano‐Stool Complexes Containing 2‐(2‐Diphenylphosphanylethyl)pyridine

Cyclopentadienyl Ruthenium(II) Complexes with Bridging Alkynylphosphine Ligands: Synthesis and Electrochemical Studies

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17. Some η 5 ‐Cyclopentadienylruthenium(II) Complexes Containing Triphenylphosphine

Cited by 172 publications

References 16 publications

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

Ruthenium‐Catalyzed β‐Alkylation of Secondary Alcohols with Primary Alcohols

Synthetic, Spectral, Structural, and Catalytic Aspects of Some Piano‐Stool Complexes Containing 2‐(2‐Diphenylphosphanylethyl)pyridine

Cyclopentadienyl Ruthenium(II) Complexes with Bridging Alkynylphosphine Ligands: Synthesis and Electrochemical Studies

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17. Some η ⁵ ‐Cyclopentadienylruthenium(II) Complexes Containing Triphenylphosphine