The nature of the metal–nitric oxide bond in the [M(CN)5(NO)]q (M=Cr, Mn, Fe, Ru, Os, and Co) and trans-[Ru(NH3)4L(NO)]q (L=pyrazine, pyridine, N2, H2O, Cl−, CN−, ) complexes: A bond-energy decomposition analysis

Lyubimova, Olga; Сизова, О. В.; Loschen, Christoph; Frenking, Gernot

doi:10.1016/j.theochem.2008.06.014

Cited by 14 publications

(6 citation statements)

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“…It was found 31 that for similar [Fe(XY)(CN) 5 ] q complexes W FeX indices correlate with the E int and E orb values calculated by EDA. Both AOSB‐A and EDA approaches suggest that the π‐component of the metal‐XY bond rises in the CN − , CO, NO series and for XY = NO the π‐back‐donation is the dominating component.…”

Section: Resultsmentioning

confidence: 87%

Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Сизова¹,

Skripnikov²,

Sokolov³

et al. 2009

Int J of Quantum Chemistry

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ABSTRACT:The atomic-orbital-symmetry based (AOSB) scheme for the decomposition of Mayer and Wiberg bond orders into -, -, and ␦-components is used to investigate different types of covalent bonds. Four series of compounds are studied: simple molecules with homonuclear bonds, inorganic molecules with polar heteronuclear bonds, [Ru(CN) 5 (XY)]q transition metal complexes with -acceptor ligands, and dimetal complexes with multiple metal-metal bonds.

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Section: Resultsmentioning

confidence: 87%

Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Сизова¹,

Skripnikov²,

Sokolov³

et al. 2009

Int J of Quantum Chemistry

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“…The linear Ru-NO bond was found to be predominantly covalent and Ru-N had a high p character, as suggested by the EDA. 37 The analysis of bond orders indicated a significant degree of p electron delocalisation over the Ru-NO group. 38 Caramori and Frenking studied some Ru II -NO complexes by EDA and concluded that the orbital term and the Pauli repulsion were responsible for the weakening or strengthening of Ru-NO bond.…”

Section: Introductionmentioning

confidence: 99%

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O

et al. 2011

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Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(κ(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl·H(2)O ((1-carboxypropyl)cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl)propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 °C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 ± 1 °C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of ∼3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl)cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at ∼8.0 and ∼11.5. Upon electrochemical reduction or under irradiation with light (λ(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO].

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“…This implies that the electron transfer between the trans ligand and NO through the π‐orbital bridge supported by Ru determines the charge and lability of NO. The nature of the Ru–NO bond in ruthenium–tetraammine–nitrosyl complexes has been investigated at the DFT level with the use of the bond‐energy decomposition analysis, which showed the importance of the π‐back donation effect and the correlation between Ru–NO and Ru–X binding interactions , …”

Section: Introductionmentioning

confidence: 99%

The Effect of trans Ligands in the NO‐Linkage Reverse Isomerization for Ruthenium–Nitrosyl–Tetraammine Complexes: A DFT Study

Yamaletdinov

Zilberberg

2017

Eur J Inorg Chem

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The nature of the metal–nitric oxide bond in the [M(CN)5(NO)]q (M=Cr, Mn, Fe, Ru, Os, and Co) and trans-[Ru(NH3)4L(NO)]q (L=pyrazine, pyridine, N2, H2O, Cl−, CN−, ) complexes: A bond-energy decomposition analysis

Cited by 14 publications

References 55 publications

Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O

The Effect of trans Ligands in the NO‐Linkage Reverse Isomerization for Ruthenium–Nitrosyl–Tetraammine Complexes: A DFT Study

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