The synthesis and reactivity of some indenyl and bis-indenyl ruthenium carbonyl complexes

Sridevi, Venugopal Shanmugham; Leong, Weng Kee

doi:10.1016/j.jorganchem.2007.07.023

Cited by 18 publications

(11 citation statements)

References 44 publications

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“…Gaede [15] has reported crystal structures of ferrocene-substituted indenyl complexes [16][17][18][19][20][21][22]. We find that synthesis of ferrocenyl indenyl ligands is the key factor for further construction of ferrocene-substituted indenyl complexes [16][17][18][19][20][21][22]. Hence, preparation of new ferrocenyl indenyl ligands is helpful for construction of their metal complexes and investigating the interactions of metallic centers.…”

Section: Introductionmentioning

confidence: 87%

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Luo

Han

Zhu

et al. 2010

Journal of Coordination Chemistry

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In this study, four ferrocenyl indenyl derivatives, C 9 H 7 -CC-Fc (1), C 9 H 7 -CC-Ph-Fc (2), C 9 H 7 -CC-Ph-CC-Fc (3), and C 9 H 7 -Ph-CC-Fc (4) (where C 9 H 7 ¼indenyl; Fc¼C 5 H 5 FeC 5 H 4 ; Ph¼C 6 H 5 ), have been synthesized by Sonogashira and Suzuki cross-coupling reactions and characterized by elemental analysis, and FT-IR, 1 H, 13 C-NMR, and MS spectroscopic methods, respectively. The molecular structures of 1, 2, and 4 were determined by X-ray single crystal diffraction. Two molecules appeared in the crystal structure of 4, and they interact through an intermolecular hydrogen bond. The electrochemical redox potential differences in 1-4 were investigated using cyclic voltammetry and calculations.

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Section: Introductionmentioning

confidence: 87%

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Luo

Han

Zhu

et al. 2010

Journal of Coordination Chemistry

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“…[15,1c] Reaction of 2-phenyl-substituted indene with Ru 3 (CO) 12 also gave the η 5 -indenyl diruthenium complex, in addition to a heptaruthenium cluster. [16] Reaction of 6 with Ru 3 (CO) 12 …”

Section: Reactions Of 2-5 With Ru 3 (Co) 12 In Xylenementioning

confidence: 99%

“…[5a,5b,5d, 16,19] The solvent effect for this kind of thermal reaction is partly decided by the reaction temperature. When ligand precursor 2 was treated with Ru 3 (CO) 12 in heptane at 140°C, complex 10 was also isolated, in addition to 21 and 22.…”

Section: Reaction Of 6 With Ru 3 (Co) 12 In Heptanementioning

confidence: 99%

“…There is only one example of a 2-phenylindenyl diruthenium complex [(η 5 -C 9 H 6 Ph)Ru(CO)(µ-CO)] 2 in which the cis meso isomer was obtained and characterized by X-ray diffraction analysis. [16] The reason why complex 17 exists as a single cis meso isomer is still not very clear. It seems that the existence of a picolyl (or phenyl) substituent on the indenyl ring may stabilize the cis meso isomer and promote its formation.…”

Section: H Nmr Spectra Analysismentioning

confidence: 99%

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Reactions of Pyridyl Side Chain Functionalized Indenes with Ru₃(CO)₁₂

Chen

Song

et al. 2008

Eur J Inorg Chem

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Reactions of the pyridyl side chain functionalized indenes 3‐R‐C9H7 [R = (C5H4N)CH2CMe2 (1), (MeC5H3N)CH2CMe2 (2), (C5H4N)CH2 (6)] with Ru3(CO)12 in refluxing xylene gave the facial coordinated indenyl cluster [μ3‐η5:η2:η2‐(C5H3N)CH2Me2C(C9H6)]Ru4(μ3‐CO)(CO)7 (8), the syn‐η5:η6‐coordinated indenyl cluster [μ‐η5:η6‐(MeC5H3N)CH2CMe2(C9H6)Ru2(CO)3]2 (10), and the η1:η2‐coordinated indenyl complex[η2‐(C5H3N)CH2(C9H7)][η1:η2‐(C5H4N)CH2(C9H6)]Ru2(CO)4(18), respectively, in addition to the normal diruthenium complexes [(η5‐RC9H6)Ru(CO)]2(μ‐CO)2 [R = (C5H4N)CH2CMe2 (7), (MeC5H3N)CH2CMe2 (9), (C5H4N)CH2 (17)]. When the pyridyl side chains were replaced by other bulky groups [R = tBu (3), PhCH2Me2C (4), (C9H6N)CH2Me2C (5)], the similar syn‐η5:η6‐coordinated indenyl clusters 12, 14, and 16 were also obtained. When 1 or 2 were treated with Ru3(CO)12 in refluxing heptane, the ionic clusters {[(C5H4N)CH2Me2C(C9H6)]Ru(CO)2}+[HRu6(CO)18]– (19), [(C5H4N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (20), and complex 8 or ionic clusters {[(MeC5H3N)CH2Me2C(C9H6)]Ru(CO)2}+[HRu6(CO)18]– (21) and [(MeC5H3N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (22) were obtained. Similar treatment of 5 or 6 with Ru3(CO)12 in refluxing heptane gave the ionic clusters [(C9H6N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (23) or {[η3‐(C5H4N)CH(C9H7)][η2‐(C5H4N)CH2(C9H7)]Ru(CO)}+[HRu6(CO)18]– (24), respectively, in addition to complex 18 in the latter case. The molecular structures of 8, 9, 10, 14, 17, 18, 21, 22, and 24 were determined by X‐ray diffraction analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…In entries 9 and 10 in Table 1 [8] and [9] respectively, were employed. In entries 9 and 10 in Table 1 [8] and [9] respectively, were employed.…”

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confidence: 99%

Ruthenium/C₅Me₅/Bisphosphine‐ or Bisphosphite‐Based Catalysts for normal‐Selective Hydroformylation

et al. 2012

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Hydroformylation of alkenes is the most widely industrially applied homogeneous transition-metal-catalyzed reaction. [1] Since the discovery by Roelen that [HCo(CO) 4 ] can promote this transformation, [2] cobalt complexes have been used extensively as hydroformylation catalysts. However, more recently developed rhodium/phosphine complexes generally afford higher selectivity compared to cobalt catalysts for the production of normal aldehydes (n-aldehydes), which are utilized as intermediates for the synthesis of plasticizers, solvents, and detergents. Additionally, rhodium complexes typically produce negligible quantities of alkanes from competing alkene hydrogenation unlike cobalt-based hydroformylation catalysts. Thus, rhodium catalysts have come to play a major role in industry.Intensive studies have been devoted both in industry and in academia to the development of bisphosphine or bisphosphite ligands that promote highly normal-selective (n-selective) rhodium-catalyzed hydroformylation of 1-alkenes. [3] However, recent global increases in demand for rhodium, particularly in the automotive industry, is increasing the price of this already expensive precious metal. [4] In contrast, more cost-effective cobalt-based systems suffer from concomitant formation of alkane by-products. Considering these factors, the development of hydroformylation catalysts using other transition metals is desirable. In contrast to the extensive studies on cobalt and rhodium systems, other transition metals such as palladium, [5] iridium [6] , and ruthenium [7] have received less attention as potential hydroformylation catalysts. We have targeted ruthenium, which is less expensive compared to rhodium. Only two examples of rutheniumcatalyzed hydroformylation with high n-selectivity (normal/ iso (n/i) > 30) have been reported. [7d,h] Our design for ruthenium hydroformylation catalysts is illustrated in Figure 1. In conventional rhodium catalysts for hydroformylation, the hydridorhodium(I) A is a key species to which alkenes insert to generate the corresponding alkylrhodium species. In contrast, the dihydrido ruthenium(II) B is known as a catalytically active species for hydrogenation of alkenes, which is a problematic side reaction in hydroformylation. By comparing the species A and B, we envisioned replacing one hydride in B with a cyclopentadienyl anion. Through this strategic change, the [CpRu II ] complex C was expected to be inactive as an alkene hydrogenation catalyst because the ruthenium center lacks one of the requisite hydride ligands present in the active hydrogenation intermediate B. Herein, we report a new catalyst system that consists of a [Cp*Ru II ] (Cp* = C 5 Me 5 ) complex ligated by chelating bisphosphines. These complexes effect the hydroformylation of 1-alkenes with the highest level of activity and n to i selectivity to date for any ruthenium-based catalyst, [7d,h] even though the activity remains well below that of the best rhodium-based catalysts. Additionally, these ruthenium catalysts successfully supp...

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The synthesis and reactivity of some indenyl and bis-indenyl ruthenium carbonyl complexes

Cited by 18 publications

References 44 publications

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru₃(CO)₁₂

Ruthenium/C₅Me₅/Bisphosphine‐ or Bisphosphite‐Based Catalysts for normal‐Selective Hydroformylation

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The synthesis and reactivity of some indenyl and bis-indenyl ruthenium carbonyl complexes

Cited by 18 publications

References 44 publications

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Synthesis and structural characterization of ferrocenyl indenyl derivatives

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12

Ruthenium/C5Me5/Bisphosphine‐ or Bisphosphite‐Based Catalysts for normal‐Selective Hydroformylation

Contact Info

Product

Resources

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Reactions of Pyridyl Side Chain Functionalized Indenes with Ru₃(CO)₁₂

Ruthenium/C₅Me₅/Bisphosphine‐ or Bisphosphite‐Based Catalysts for normal‐Selective Hydroformylation