A five-coordinate ruthenium(II)–porphyrin–carbene complex: [bis(3-trifluoromethylphenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ4N)ruthenium(II)

Wada, Satoko; Yuge, Hidetaka; Miyamoto, Takeshi

doi:10.1107/s010827010301669x

Cited by 6 publications

(3 citation statements)

References 8 publications

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“…A similar situation has been previously observed with other porphyrin ruthenium complexes . The Ru−N distances of 2.042(3)−2.054(3) Å all fall within the range previously reported for diamagnetic ruthenium porphyrin complexes. ,,– The geometry of the coordination sphere is close to an octahedral geometry. Bond angles at ruthenium are in the range 90.02(14)−96.39(14)° for cis angles and 173.08(12)−173.58 (12)° for trans angles.…”

Section: Resultssupporting

confidence: 87%

“…The Ru−C distance of 1.839(4) Å is slightly longer than the ruthenium−carbon double bond (1.829(9) Å) for (TPP)Ru[C(CO 2 Et][MeOH] reported by us some years ago and similar to those reported by Che and Miyamoto. ,– The Ru−O (THF) distance 2.376(3) Å is shorter than the axial Os−O bond (THF, 2.43(2) Å) in a similar carbene osmium complex, reported by Woo et al, as expected from the different size of the two metal atoms.…”

Section: Resultssupporting

confidence: 79%

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Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

et al. 2008

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The new (porphyrin)ruthenium(II) carbene complex 1 has been prepared by treating (TPP)Ru(CO)(EtOH) with excess 2,6-di-tert-butyl-4-methylphenyl diazoacetate and characterized by X-ray crystal structure analysis due to a kinetic stability. The reactivity of 1 toward axial ligands (CO, pyridine, dimethylphenylphosphine) and the asymmetric cyclopropanation of styrene with this bulky diazoacetate ester catalyzed by ruthenium Halterman porphyrin are also presented.

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Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 79%

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

et al. 2008

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“…This has led to the formation of an organometallic complex, [Ru(η 3 -C 4 ,N 3 ,S-L 1 )(η 2 -P,P-dppm)(η 1 -P-dppm)] ( 1 ) (Figure ). The Ru1−C3 bond length of 2.076(3) Å is comparable with the literature reports . The angles around the Ru II center reveal severely distorted octahedral geometry {N1−Ru−S1, 79.21(8)°; trans angles P1−Ru−P3, P4−Ru−N, and S−Ru−C3 of 174.36(3)°, 161.92(9)°, and 156.92(11)°, respectively}.…”

Section: Resultssupporting

confidence: 85%

Bis(diphenylphosphino)methane Induces Unusual Cyclometalation of Thiophene and Phenyl Rings (R) at the C² Carbon of Thiosemicarbazones {R-C²(H) = N³-N² H-C(═S)-N¹H₂} in Ruthenium(II) Complexes

et al. 2007

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Reaction of trans-[Ru(dppm)2Cl2] (dppm = Ph2PCH2PPh2) with thiophene-2-carbaldehyde thiosemicarbazone {C4H3S-C2(H)N3-N2H-C1(S)-N1H2, H2L1} in the presence of Et3N base formed a complex, [Ru(η3-C,N3,S-L1)(η2-P,P-dppm)(η1-P-dppm)] (1) (L1 is dinegative thiophene-2-carbaldehyde thiosemicarbazonate), with an unprecedented cyclometalation of a heterocyclic ring in RuII-thiosemicarbazone chemistry. In contrast, the thiophene ring did not undergo cyclometalation in complexes of monotertiary phosphines of stoichiometry [Ru(η2-N2,S-HL1)2(PR′3)2] (R′ = phenyl, 2; p-tolyl, 3; HL1 = uninegative thiophene-2-carbaldehyde thiosemicarbazonate). Benzaldehyde thiosemicarbazone {C6H5-C(H)N3-N2H-C(S)-N1H2,H2L2} with trans-[Ru(dppm)2Cl2] displayed cyclometalation and yielded an organometallic complex [Ru(η3-C,N3,S-L2)(η2-P,P-dppm)(η1-P-dppm)] (4) (L2 is dinegative benzaldehyde thiosemicarbazonate), similar to complex 1. The complexes have been characterized using analytical, spectroscopic, and single-crystal X-ray crystallographic (1, 3, 4) studies. The cyclometalation in complexes 1 and 4 is attributed to the presence of two types of coordination modes of dppm, namely, both η1-P-dppm and chelating η2-P,P-dppm in the same complex. These cyclometalation reactions represent the first examples in RuII-thiosemicarbazone chemistry.

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Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

Huang

et al. 2004

Chemistry A European J

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A wide variety of ruthenium porphyrin carbene complexes, including [Ru(tpfpp)(CR(1)R(2))] (CR(1)R(2) = C(p-C(6)H(4)Cl)(2) 1 b, C(p-C(6)H(4)Me)(2) 1 c, C(p-C(6)H(4)OMe)(2) 1 d, C(CO(2)Me)(2) 1 e, C(p-C(6)H(4)NO(2))CO(2)Me 1 f, C(p-C(6)H(4)OMe)CO(2)Me 1 g, C(CH==CHPh)CO(2)CH(2)(CH==CH)(2)CH(3) 1 h), [Ru(por)(CPh(2))] (por=tdcpp 2 a, 4-Br-tpp 2 b, 4-Cl-tpp 2 c, 4-F-tpp 2 d, tpp 2 e, ttp 2 f, 4-MeO-tpp 2 g, tmp 2 h, 3,4,5-MeO-tpp 2 i), [Ru(por)[C(Ph)CO(2)Et]] (por=tdcpp 2 j, tmp 2 k), [Ru(tpfpp)(CPh(2))(L)] (L = MeOH 3 a, EtSH 3 b, Et(2)S 3 c, MeIm 3 d, OPPh(3) 3 e, py 3 f), and [Ru(tpfpp)[C(Ph)CO(2)R](MeOH)] (R = CH(2)CH==CH(2) 4 a, Me 4 b, Et 4 c), were prepared from the reactions of [Ru(por)(CO)] with diazo compounds N(2)CR(1)R(2) in dichloromethane and, for 3 and 4, by further treatment with reagents L. A similar reaction of [Os(tpfpp)(CO)] with N(2)CPh(2) in dichloromethane followed by treatment with MeIm gave [Os(tpfpp)(CPh(2))(MeIm)] (3 d-Os). All these complexes were characterized by (1)H NMR, (13)C NMR, and UV/Vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1 d, 2 a,i, 3 a, b, d, e, 4 a-c, and 3 d-Os revealed Ru==C distances of 1.806(3)-1.876(3) A and an Os==C distance of 1.902(3) A. The structure of 1 d in the solid state features a unique "bridging" carbene ligand, which results in the formation of a one-dimensional coordination polymer. Cyclic voltammograms of 1 a-c, g, 2 a-d, g-k, 3 b-d, 4 a, b, and 3 d-Os show a reversible oxidation couple with E(1/2) values in the range of 0.06-0.65 V (vs Cp(2)Fe(+/0)) that is attributable to a metal-centered oxidation. The influence of carbene substituents, porphyrin substituents, and trans-ligands on the Ru==C bond was examined through comparison of the chemical shifts of the pyrrolic protons in the porphyrin macrocycles ((1)H NMR) and the M==C carbon atoms ((13)C NMR), the potentials of the metal-centered oxidation couples, and the Ru==C distances among the various ruthenium porphyrin carbene complexes. A direct comparison among iron, ruthenium, and osmium porphyrin carbene complexes is made.

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A five-coordinate ruthenium(II)–porphyrin–carbene complex: [bis(3-trifluoromethylphenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ⁴N)ruthenium(II)

Cited by 6 publications

References 8 publications

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Bis(diphenylphosphino)methane Induces Unusual Cyclometalation of Thiophene and Phenyl Rings (R) at the C² Carbon of Thiosemicarbazones {R-C²(H) = N³-N² H-C(═S)-N¹H₂} in Ruthenium(II) Complexes

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

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A five-coordinate ruthenium(II)–porphyrin–carbene complex: [bis(3-trifluoromethylphenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ4N)ruthenium(II)

Cited by 6 publications

References 8 publications

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Bis(diphenylphosphino)methane Induces Unusual Cyclometalation of Thiophene and Phenyl Rings (R) at the C2 Carbon of Thiosemicarbazones {R-C2(H) = N3-N2 H-C(═S)-N1H2} in Ruthenium(II) Complexes

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

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A five-coordinate ruthenium(II)–porphyrin–carbene complex: [bis(3-trifluoromethylphenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ⁴N)ruthenium(II)

Bis(diphenylphosphino)methane Induces Unusual Cyclometalation of Thiophene and Phenyl Rings (R) at the C² Carbon of Thiosemicarbazones {R-C²(H) = N³-N² H-C(═S)-N¹H₂} in Ruthenium(II) Complexes