Synthesis and characterization of two ruthenium(II) heteroleptic complexes of annelated derivatives of 2,2′-bipyridine

Amouyal, Edmond; Penaud–Berruyer, Florence; Azhari, Driss; Aït‐Haddou, Hassan; Fontenas, Christophe; Bejan, Elena; Daran, Jean‐Claude; Balavoine, G.

doi:10.1039/a708740c

Cited by 7 publications

(3 citation statements)

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“…1 H NMR (CD3CN): δH 2.40 (s, 3H), 2.51-3.02 (m, 12H), 7.71 (dd, J ) 4.58 and 1.53, 4H), 7.79 (dd, J ) 5.50 and 1.53, 4H), 8.68 (dd, J ) 5.20 and 1.23, 4H), 8.75 (dd, J ) 4.28 and 1.53, 4H). FAB MS, m/z (%): 779 (40) [M + -PF6], 634 (18) [M + -2PF6], 593 (10) [M + -2PF6 -NCMe], 478 (12) [M + -2PF6bpy]. Anal.…”

Section: Syntheses [([9]anes3)ru(py)3][pf6]2mentioning

confidence: 99%

“…Previous synthetic strategies for the synthesis of heteroleptic ruthenium(II) complexes have involved using bidentate , and tridentate ligands. Using the previously reported [Ru(DMSO)Cl 2 ([9]aneS 3 )], we have developed a methodology to control the substitution chemistry of facially coordinated N-donor ligands around the [Ru([9]aneS 3 )] 2+ metal center.…”

Section: Introductionmentioning

confidence: 99%

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Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center

et al. 2000

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The complex [Ru(py)3([9]aneS3)][PF6]2, 1 (py = pyridine), has proved to be a suitable starting material for the synthesis of heteroleptic Ru(II) complexes. By exploiting unfavorable steric interactions between 2-H and 6-H hydrogens of coordinated pyridyl ligands, we have synthesized half-sandwich complexes incorporating the thiocrown [9]aneS3 and a variety of facially coordinated N-donor ligands. Such complexes are easily prepared: Stirring 1 at room temperature in the presence of a suitable nitrile ligand leads to the exclusive substitution of one py ligand to produce complexes such as [([9]aneS3)Ru(py)2(NCMe)][PF6]2, 2. However, if the same reaction is carried out at higher temperatures, two py ligands are substituted, leading to complexes such as [([9]aneS3)Ru(py)(NCMe)2][PF6]2, 3. An alternative approach to such heteroleptic species has also been developed which exploits the restricted ability of thioethers to neutralize positive charges through sigma-donation. This phenomenon allows the synthesis of heteroleptic complexes in a two-step procedure via monocationic species. By variation of the donor/acceptor properties of ligands incorporated into the [Ru([9]aneS3)]2+ metal center, it is possible to tune the Ru(III)/Ru(II) redox couple over a range of > 700 mV. The solid-state structures of 1-3 were confirmed by X-ray crystallography studies. Crystal data: C22H30F12N4O2P2RuS3 (1.CH3NO2), monoclinic, Cc, a = 23.267(5) A, b = 11.5457(18) A, c = 26.192(5) A, alpha = 90 degrees, beta = 114.836(10) degrees, gamma = 90 degrees, Z = 8; C18H25F12N3P2RuS3 (2), triclinic, P1, a = 11.3958(19) A, b = 11.4280(19) A, c = 11.930(2) A, alpha = 100.518(3) degrees, beta = 100.542(3) degrees, gamma = 112,493(3) degrees, Z = 2; C15H23F12N3P2RuS3 (3), orthorhombic, Pna2(1)), a = 14.748(5) A, b = 18.037(18) A, c = 10.341(5) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, Z = 4.

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Section: Syntheses [([9]anes3)ru(py)3][pf6]2mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center

et al. 2000

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“…The use of lithium diisopropylamide (LDA) or potassium tert-butoxide (tBuOK) as formation of the isomer 13 in good yield (70%). [10] However, the same reaction in acetic acid in the presence of am-bases at Ϫ20°C gave 12 in similar yields.…”

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confidence: 88%

Synthesis of Highly Soluble Annelated Polypyridines

et al. 1999

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Ruthenium and Osmium: Low Oxidation States

Housecroft

2003

Comprehensive Coordination Chemistry II

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Synthesis and characterization of two ruthenium(II) heteroleptic complexes of annelated derivatives of 2,2′-bipyridine

Cited by 7 publications

References 21 publications

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center

Synthesis of Highly Soluble Annelated Polypyridines

Ruthenium and Osmium: Low Oxidation States

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Synthesis and characterization of two ruthenium(II) heteroleptic complexes of annelated derivatives of 2,2′-bipyridine

Cited by 7 publications

References 21 publications

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS3)]2+ Metal Center

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS3)]2+ Metal Center

Synthesis of Highly Soluble Annelated Polypyridines

Ruthenium and Osmium: Low Oxidation States

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Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center

Controlling Substitution Chemistry in Ruthenium(II) Systems. Synthesis of Heteroleptic Complexes Incorporating the [Ru([9]aneS₃)]²⁺ Metal Center