Computational DFT Study of Ruthenium Tetracarbonyl Polymer

Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

doi:10.1021/ct800407h

Cited by 36 publications

(37 citation statements)

References 46 publications

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“…. These values are smaller than those reported for metal-metal single bonds in [Ru(CO)4]8 (0.70) and Ru3(CO)12 (0.62),50 but they are similar to those reported for [((C5H4NH)2Fe)Ru(PR3)2] (PR3 = PPh3, 0.28, and PMe2Ph, 0.26) 24. …”

supporting

confidence: 49%

Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds

et al. 2016

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The reaction of [Pd(dtbpf)Cl 2 ] (dtbpf = 1,1′-bis(di-tertbutylphosphino)ferrocene) with sodium bromide yields [Pd(dtbpf)Br][Br], which displays an interaction between the iron and palladium atoms. The structure of this compound has been obtained and is compared to those of the previously reported [Pd(dtbpf)X] + (X = Cl, I) analogues. Similar to [Pd(dtbpf)Cl] + , [Pd(dtbpf)Br] + appears to undergo a solid-state isomerization at low temperature to a species in which the Fe−Pd interaction is disrupted. In addition to 1 H and 31 P{ 1 H} NMR and visible spectroscopy, the [Pd(dtbpf)X] + (X = Cl, Br) compounds were also characterized by zero-field 57 Fe Mossbauer spectroscopy. DFT calculations on [Pd(dtbpf)-X] + (X = Cl, Br, I) show that the Fe−Pd interaction is weak and noncovalent and that the strength of the interaction decreases as the halide becomes larger. A related trend is noted in the potential at which oxidation of the iron center occurs; the larger the halide, the less positive the potential at which oxidation occurs. Finally, the catalytic activity of [Pd(dtbpf)X] + (X = Cl, Br, I) in the arylation of an aromatic ketone was examined and compared to the activity of [Pd(dtbpf)Cl 2 ].

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supporting

confidence: 49%

Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds

et al. 2016

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“…The standard all-electron basis set 6-31 G (d) was used for non-metal atoms, while Huzinaga's allelectron basis set [41] with an additional p-polarization function (433321/4331/421) was used for ruthenium. Huzinaga's all-electron basis set has been found in earlier studies to be stable and also to describe ligand-unsupported ruthenium systems reliably [37,38,42]. However, to verify the reliability of the AE basis set, we performed tests with a relativistic ECP basis set (LANL2DZ).…”

Section: Methodsmentioning

confidence: 99%

“…Our group has previously studied unsupported ruthenium chains, such as [Ru(CO) 4 ] n and [Ru(bpy)(CO) 2 ] n which are formed via direct Ru-Ru bonding [37,38]. In the current study, our aim was to investigate the geometry and M-M interactions of ruthenium string complexes, especially the as yet not synthesized [Ru 7 (tpta) 4 Cl 2 ] and [Ru 9 (ppta) 4 Cl 2 ], and to compare the string complexes and unsupported ruthenium chains.…”

Section: Introductionmentioning

confidence: 99%

Metal–metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

2011

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Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

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“…The basis for Ru (optimised for a mixed oxide RuSr 2 GdCu 2 O 8 ) was taken from M. Towler's web page (University of Cambridge); 58 the same basis was used in a recent study of ruthenium-tetracarbonyl polymers. 59 The rutile (110) surface was modelled using a (2 Â 6) slab with two O-Ti-O trilayers (6 atomic layers). Fig.…”

Section: Electronic Structure Calculationsmentioning

confidence: 99%

Adsorption and electron injection of the N3 metal–organic dye on the TiO2 rutile (110) surface

Martsinovich

Ambrosio

Troisi

2012

Phys. Chem. Chem. Phys.

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Metal-organic ruthenium-based dyes are often used as a source of photogenerated electrons in dye-sensitised solar cells and photocatalysis. Here, we study the relationship between adsorption geometry and electron injection properties of one of the most successful metal-organic dyes, N3 (cis-bis(isothiocyanato)-bis(4,4'-dicarboxy-2,2'-bipyridyl)-ruthenium(II)), on the TiO(2) rutile (110) surface. We systematically construct all possible adsorption configurations of the N3 molecule on this surface. By combining density-functional theory calculations and electron transfer calculations, we find that a large number of adsorption configurations are possible--more than ten structures, which differ in the number of carboxylic and thiocyanate groups adsorbed and in the adsorption mode of the carboxylic groups, have similar adsorption energies and similar electron injection times. Therefore, the observed fast electron injection from this dye may originate either from one adsorption configuration or from several co-existing configurations. Our results suggest that related substituted metal-organic dyes with fewer anchoring groups will also have good electron injection properties, even if only a small subset of adsorption configurations is available for them.

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Computational DFT Study of Ruthenium Tetracarbonyl Polymer

Cited by 36 publications

References 46 publications

Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds

Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds

Metal–metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

Adsorption and electron injection of the N3 metal–organic dye on the TiO2 rutile (110) surface

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Computational DFT Study of Ruthenium Tetracarbonyl Polymer

Cited by 36 publications

References 46 publications

Structural, Computational, and Spectroscopic Investigation of [Pd(κ3-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]+ (X = Cl, Br, I) Compounds

Structural, Computational, and Spectroscopic Investigation of [Pd(κ3-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]+ (X = Cl, Br, I) Compounds

Metal–metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

Adsorption and electron injection of the N3 metal–organic dye on the TiO2 rutile (110) surface

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Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds

Structural, Computational, and Spectroscopic Investigation of [Pd(κ³-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]⁺ (X = Cl, Br, I) Compounds