Ruthenium Carbonyl Complexes of N-Heterocyclic Molecules. Part 2. Preparation, Protonation and Decarbonylation Reactions of Complexes with a Bidentate Terpyridyl Ligand. Structure of [Ru(CO)2(phen)(tpyH)](BF4)3

Thomas, Nicholas C.; Fischer, Jean

doi:10.1080/00958979009409180

Cited by 31 publications

(10 citation statements)

References 10 publications

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“…Purification by column chromatography (neutral alumina, 1:3 (v/v) CH 3 CN/toluene as eluent) prior to recrystallization (slow diffusion of Et 2 O into a CH 3 CN solution) was needed to obtain analytically pure [(tpy)(bpy)RuC⋮CR] + salts. The desired product [(tpy)(bpy)RuC⋮CR] + was eluted as a purple band, followed by an orange band, which was characterized as [(tpy)(bpy)Ru(N⋮CCH 3 )] 2+ 12f. We have attempted to improve the product yield by varying the amount of HC⋮CR and Et 3 N, but no significant improvement was found.…”

Section: Resultsmentioning

confidence: 99%

“…The more positive E 1/2 values of the redox couples for 9 and 10 compared to 1 − 8 can be rationalized by the increase in electronic charge in the complexes. In the literature, the electrochemical behavior of ruthenium-polypyridyl complexes with the general formula [Ru(tpy)(bpy)L] n + have been extensively studied. , Complexes of this type show reduction waves corresponding to successive reduction at the polypyridyl ligands. The tpy ligand is preferentially reduced because its π* level is lower than that of bpy.…”

Section: Discussionmentioning

confidence: 99%

“…The irreversible oxidation waves for 1 − 8 are assigned as metal-centered, because the coordinated tpy or bpy ligands in [Ru(tpy)(bpy)L] n + are not oxidized at around this potential. Comparing the reported Ru(III/II) redox potentials of [Ru(tpy)(bpy)L] + (L = - Cl,12c - NCNAr,30b and - C⋮N: 12e E 1/2 = 0.41, 0.34−0.43, and 0.67 V, respectively) and E pa of [Ru(tpy)(bpy)C⋮CR] + (0.15 to 0.26 V), [Ru(tpy)(bpy)C⋮CR] + is clearly more easily oxidized. It is interesting to compare the Ru(III/II) waves for [Ru(tpy)(bpy)C⋮CR] + and [Ru(tpy)(bpy)C⋮N] + , because - C⋮CR and - C⋮N are isoelectronic and both ligands can coordinate with metal centers through σ-bonding and π-back-bonding interactions.…”

Section: Discussionmentioning

confidence: 99%

“…We therefore initiated a program directed toward the synthetic chemistry of organoruthenium complexes based on polypyridyl ancillary ligands. Significantly, reports on the preparation and characterization of tpy-bpy ruthenium derivatives bearing organometallic-type ligands are conspicuous by their rarity . We now describe the synthesis of a series of acetylide- and carbene-ruthenium complexes containing the bpy and tpy auxiliaries.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium(II) σ-Acetylide and Carbene Complexes Supported by the Terpyridine−Bipyridine Ligand Set: Structural, Spectroscopic, and Photochemical Studies

et al. 2004

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A series of acetylide-and carbene-ruthenium complexes containing polypyridine ligands, [(tpy)(bpy)RuCtCR] + (tpy ) 2,2′:6′,2′′-terpyridine, bpy ) 2,2′-bipyridine; R ) C 6 H 4 F-4 (1), C 6 H 4 Cl-4 (2), C 6 H 5 (3), C 6 H 4 Me-4 (4), C 6 H 4 OMe-4 (5), t-Bu (6), (C 6 H 4 CtC) n C 6 H 5 [n ) 1 (7) and 2 (8)]) and [(tpy)(bpy)RudC(OMe)(CH 2 R)] 2+ (R ) C 6 H 4 OMe-4 (9), t-Bu (10)) have been prepared. The molecular structures of 4(PF 6 ), 5(PF 6 ), and 9(ClO 4 ) 2 reveal Ru-C distances of 2.025(9), 2.025(7), and 1.933(6) Å, respectively. The Ru(III/II) oxidation waves are irreversible for 1-8 (E pa ) 0.15-0.26 V vs FeCp 2 +/0 ) but reversible for 9 and 10 (E 1/2 ) 0.99 and 1.00 V, respectively). The absorption bands in the visible region for 1-8 (λ max ) 502-526 nm) and 9 and 10 (λ max ca. 410 nm) are assigned as d π (Ru II ) f π*(polypyridine) MLCT transitions. Complexes 1-8 weakly emit at λ max ) 748-786 nm in CH 3 CN solution at 298 K (λ ex ) 550 nm). Complexes 9 and 10 are nonemissive in CH 2 Cl 2 solution at 298 K, but in glassy n-butyronitrile at 77 K, excitation at λ ) 415 nm produces emission at λ max ) 597 and 615 nm, respectively. These emissions are tentatively ascribed as d π (Ru II ) f π*(polypyridyl) 3 MLCT in nature. The carbene derivatives 9 and 10 undergo photochemical reactions upon irradiation in solution, and [(tpy)(bpy)RuNtCCH 3 ] 2+ and 4-methoxybenzaldehyde were isolated from the photolysis of 9 in CH 3 CN.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ruthenium(II) σ-Acetylide and Carbene Complexes Supported by the Terpyridine−Bipyridine Ligand Set: Structural, Spectroscopic, and Photochemical Studies

et al. 2004

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“…Several examples of coordination with Ru(II) are known in which tpy does not utilize its maximum denticity. Two of these complexes are of the type [Ru(CO) 2 (LL)(tpy- N , N )] 2+ , where LL = Br, Br or LL = 1,10-phenanthroline . Group VI metals are also known to from bidentate tpy complexes of the type [M(CO) 4 (tpy- N , N )] …”

Section: Introductionmentioning

confidence: 99%

Formation of Ruthenium(II) Complexes with Unsymmetrical Terdentate Ligands

1997

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Three unsymmetrical terdentate ligands, 2-(2'-quinolyl)-1,10-phenanthroline (4), 2-(1'-isoquinolyl)-1,10-phenanthroline (5), and 3,3'-dimethylene-2-(2'-quinolyl)-1,10-phenanthroline (6), have been prepared by application of the Friedländer condensation. Ligand 4 forms predominantly a pentaaza-coordinated (N5) complex with Ru(II), [Ru(4-N,N',N")(4-N,N')Cl](PF(6)), whose structure was determined by X-ray analysis (C(42)H(26)ClF(6)N(6)PRu: monoclinic, C2/c, a = 29.308(3) Å, b = 15.205(2) Å, c = 19.505(2) Å, beta = 107.312(8) degrees, V = 8298(1) Å(3), Z = 8). Ligand 5 forms predominantly a hexaaza-coordinated (N6) complex, [Ru(5-N,N',N")(2)](PF(6))(2). The bridged species 6 shows intermediate behavior, and the rate for interconversion of the N5 to N6 complex has been measured. The stereochemical features of these two binding modes are examined, and both pi-stacking and steric effects are invoked to explain the observed behavior, leading to the proposal of a backside displacement mechanism for their interconversion.

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Insertion Reactions into Palladium–Carbon Bonds of Complexes Containing Terdentate Nitrogen Ligands; Experimental and Ab initio MO Studies

Groen

Zwart

Vlaar

et al. 1998

Eur. J. Inorg. Chem.

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Novel methyl complexes [Pd(Me)(N‐N‐N)]X (N‐N‐N = flexible or rigid terdentate nitrogen ligand, X = Cl, SO3CF3, BAr′4) have been synthesized and fully characterized. All complexes readily underwent insertion of carbon monoxide resulting in the quantitative formation of complexes [Pd{C(O)Me}(N‐N‐N)]X [X = Cl (1d–6d), BAr′4 (1e–6e)]. Subsequently, complexes 2e–6e underwent quantitative insertion of norbornadiene, resulting in complexes [Pd{C7H8C(O)Me}(N‐N‐N)]BAr′4 (2f–6f). Unexpectedly, these complexes, including even those containing rigid terdentate nitrogen ligands, possess a structure in which the nitrogen ligand is coordinated in a bidentate fashion. A kinetic study of the reaction of norbornadiene with complexes 1e–6e revealed that the reactivity of complexes 1e–6e toward norbornadiene increases with increasing rigidity of the terdentate ligand, i.e. with increasing strain in the PdN3 moiety, which indicates that insertion very likely occurs via a mechanism involving nitrogen dissociation. This is fully supported by ab initio MO calculations on CO and ethylene insertion into carbon–palladium bonds of cationic model systems containing a rigid terdentate nitrogen ligand, which showed that the lowest‐energy pathway for both insertion reactions consists of substitution of one of the distal nitrogen atoms of the rigid terdentate nitrogen ligand by the substrate, followed by a rate‐determining migratory insertion of the substrate into the carbon–palladium bond.

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Ruthenium Carbonyl Complexes of N-Heterocyclic Molecules. Part 2. Preparation, Protonation and Decarbonylation Reactions of Complexes with a Bidentate Terpyridyl Ligand. Structure of [Ru(CO)₂(phen)(tpyH)](BF₄)₃

Cited by 31 publications

References 10 publications

Ruthenium(II) σ-Acetylide and Carbene Complexes Supported by the Terpyridine−Bipyridine Ligand Set: Structural, Spectroscopic, and Photochemical Studies

Ruthenium(II) σ-Acetylide and Carbene Complexes Supported by the Terpyridine−Bipyridine Ligand Set: Structural, Spectroscopic, and Photochemical Studies

Formation of Ruthenium(II) Complexes with Unsymmetrical Terdentate Ligands

Insertion Reactions into Palladium–Carbon Bonds of Complexes Containing Terdentate Nitrogen Ligands; Experimental and Ab initio MO Studies

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