Comparison of (triphenylphosphine)ruthenium complexes containing the 2,2′:6′,2′′-terpyridine (trpy) and 4,4′,4′′-tri-t-butyl-2,2′:6′,2′′-terpyridine (trpy*) ligands

Billings, Susan B.; Mock, Michael T.; Wiacek, Kevin; Turner, Melinda; Kassel, W. Scott; Takeuchi, Kenneth J.; Rheingold, Arnold L.; Boyko, Walter J.; Bessel, Carol A.

doi:10.1016/s0020-1693(03)00300-1

Cited by 14 publications

(4 citation statements)

References 43 publications

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“…38 The aromatic ring protons in the bound PPh 3 ligands of each Au 11 cluster exhibit three distinct multiplet peaks with chemical shifts between 7.4 and 6.6 ppm that result from differential shielding of the protons in the ortho, meta, and para positions of the ligand upon binding to the metal. 39 The integration of the peaks matches the expected 2:2:1 ratio in both compounds. The larger downfield chemical shift for the ortho protons and larger chemical shift difference between peaks in the Au11−7 spectra suggest that the electronic environment of the ligands in Au11−7 is impacted by the Au core to a greater extent than in Au11−8.…”

Section: ■ Results and Discussionsupporting

confidence: 63%

“…The aromatic ring protons in the bound PPh 3 ligands of each Au 11 cluster exhibit three distinct multiplet peaks with chemical shifts between 7.4 and 6.6 ppm that result from differential shielding of the protons in the ortho, meta, and para positions of the ligand upon binding to the metal . The integration of the peaks matches the expected 2:2:1 ratio in both compounds.…”

Section: Resultsmentioning

confidence: 67%

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Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

2014

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Ligand exchange is frequently used to introduce new functional groups on the surface of inorganic nanoparticles or clusters while preserving the core size. For one of the smallest clusters, triphenylphosphine (TPP)-stabilized undecagold, there are conflicting reports in the literature regarding whether core size is retained or significant growth occurs during exchange with thiol ligands. During an investigation of these differences in reactivity, two distinct forms of undecagold were isolated. The X-ray structures of the two forms, Au11(PPh3)7Cl3 and [Au11(PPh3)8Cl2]Cl, differ only in the number of TPP ligands bound to the core. Syntheses were developed to produce each of the two forms, and their spectroscopic features correlated with the structures. Ligand exchange on [Au11(PPh3)8Cl2]Cl yields only small clusters, whereas exchange on Au11(PPh3)7Cl3 (or mixtures of the two forms) yields the larger Au25 cluster. The distinctive features in the optical spectra of the two forms made it possible to evaluate which of the cluster forms were used in the previously published papers and clarify the origin of the differences in reactivity that had been reported. The results confirm that reactions of clusters and nanoparticles may be influenced by small variations in the arrangement of ligands and suggest that the role of the ligand shell in stabilizing intermediates during ligand exchange may be essential to preventing particle growth or coalescence.

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Section: ■ Results and Discussionsupporting

confidence: 63%

Section: Resultsmentioning

confidence: 67%

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

2014

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“…This was not observed for trans-RuCl 2 (tepy)(PPh 3 ) [13]. From the spectroscopic data, we can concludethat the complexes can exist in mer-and fac-isomers in solution as shown in Scheme 2.…”

Section: Ir and Nmr Studies Reactionsof M(co)mentioning

confidence: 80%

Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine

Khalil

Al-Seif²

2008

International Journal of Inorganic Chemistry

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Recommended by Wolfgange LinertReaction of M(CO) 6 ; M = Mo or W with isatin in the presence of triphenylphosphine in THF under reduced pressure gave the tricarbonyl derivatives complexes [M(CO) 3 (isatH)(PPh 3 )]. The two complexes were characterized by elemental analysis, infrared, mass and 1 H NMR spectroscopy. The spectroscopic studies show that the two complexes exist in fac-and merisomers in solutions through exchange the CO group and PPh 3 . The Uv-Vis spectra of the complexes in different solvents were studied.

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“…The hydride complexes (Series B) were synthesized from the corresponding A series complexes and an excess of NaBH 4 in ethanol (10:1) at 50 °C, resulting in the substitution of the chloride by hydride [52] (scheme 1). This differs from the procedure reported in the literature for related analogs with terpyridine substituted by tert-butyl groups [53]. The intermediate complexes were initially obtained as Cl -salts and subsequently precipitated as PF 6 -salts.…”

Section: Synthesismentioning

confidence: 89%

Synthesis and characterization of ruthenium(II) complexes incorporating 4′-phenyl-terpyridine and triphenylphosphine

Moya

López

Pérez-Zúñiga

et al. 2015

Journal of Coordination Chemistry

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The syntheses of two new series of ruthenium(II) complexes incorporating substituted 4′-phenylterpyridine, triphenylphosphine and chloride (A Series) or hydride (B Series) are reported. In both series 4′-phenyl-terpyridine incorporated substituents of varying electronic character at the 4-position: 4`-(4-chlorophenyl)-2,2´:6´,2``-terpyridine (ClPh-tpy); 4`-(4-nitrophenyl)-2,2´:6´,2``-terpyridine (NO 2 Ph-tpy) and 4`-(4-methoxyphenyl)-2,2´:6´,2``-terpyridine (OMePh-tpy). The complexes have been characterized by elemental analysis and UV-Vis, IR and NMR spectroscopy and their electrochemical properties studied. The substituents on the 4′-phenylterpyridine ligand influence the properties of the metal center. For all complexes prepared, λ max of a characteristic low energy band in the UV-Vis spectrum was found to move to shorter wavelengths as the solvent polarity increased (a hypsochromic shift). For the B series complexes, the low energy band was broader and undergoes a small shift to lower frequencies as a result of the substitution of chloride by a hydride. The 1 H-and 31 P-NMR spectra clearly indicate that the geometry of the 4′-phenyl-terpyridine ligand is meridional in the complexes, with the two triphenylphosphines trans to each other. Upon optimization of the experimental procedures the yields increased to 70% for the B series complexes.

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Comparison of (triphenylphosphine)ruthenium complexes containing the 2,2′:6′,2′′-terpyridine (trpy) and 4,4′,4′′-tri-t-butyl-2,2′:6′,2′′-terpyridine (trpy*) ligands

Cited by 14 publications

References 43 publications

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine

Synthesis and characterization of ruthenium(II) complexes incorporating 4′-phenyl-terpyridine and triphenylphosphine

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Comparison of (triphenylphosphine)ruthenium complexes containing the 2,2′:6′,2′′-terpyridine (trpy) and 4,4′,4′′-tri-t-butyl-2,2′:6′,2′′-terpyridine (trpy*) ligands

Cited by 14 publications

References 43 publications

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au11(PPh3)7Cl3and [Au11(PPh3)8Cl2]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au11(PPh3)7Cl3and [Au11(PPh3)8Cl2]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine

Synthesis and characterization of ruthenium(II) complexes incorporating 4′-phenyl-terpyridine and triphenylphosphine

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Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione

Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways with Glutathione