Improved model core potentials for the second‐ and third‐row transition metals

Lovallo, Christopher C.; Kłobukowski, Mariusz

doi:10.1002/jcc.20044

Cited by 29 publications

(19 citation statements)

References 43 publications

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“…Geometries were optimized using restricted B3LYP with the 6-31G* basis set for the main group elements. A scalar relativistic model core potential (first 30 electrons) was used for ruthenium, with the valence orbital set (5s and 4d) being of triple-zeta quality [46, 47]. Spherical harmonic d orbitals were used in all calculations and the default grid size was used for numerical integration in DFT.…”

Section: Methodsmentioning

confidence: 99%

Ruthenium dihydroxybipyridine complexes are tumor activated prodrugs due to low pH and blue light induced ligand release

Hufziger

Thowfeik

Charboneau

et al. 2014

Journal of Inorganic Biochemistry

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Ruthenium drugs are potent anti-cancer agents, but inducing drug selectivity and enhancing their modest activity remain challenging. Slow Ru ligand loss limits the formation of free sites and subsequent binding to DNA base pairs. Herein, we designed a ligand that rapidly dissociates upon irradiation at low pH. Activation at low pH can lead to cancer selectivity, since many cancer cells have higher metabolism (and thus lower pH) than non-cancerous cells. We have used the pH sensitive ligand, 6,6′-dihydroxy-2,2′-bipyridine (66′bpy(OH)2), to generate [Ru(bpy)2(66′(bpy(OH)2)]2+, which contains two acidic hydroxyl groups with pKa1 = 5.26 and pKa2 = 7.27. Irradiation when protonated leads to photo-dissociation of the 66′bpy(OH)2 ligand. An in-depth study of the structural and electronic properties of the complex was carried out using X-Ray crystallography, electrochemistry, UV/visible spectroscopy, and computational techniques. Notably, Ru-N bond lengths in the 66′bpy(OH)2 complex are longer (by ~0.3 Å) than in polypyridyl complexes that lack 6 and 6′ substitution. Thus, the longer bond length predisposes the complex for photo-dissociation and leads to the anti-cancer activity. When the complex is deprotonated, the 66′bpy(O−)2 ligand molecular orbitals mix heavily with the ruthenium orbitals, making new mixed metal-ligand orbitals that lead to a higher bond order. We investigated the anti-cancer activities of [Ru(bpy)2(66′(bpy(OH)2)]2+, [Ru(bpy)2(44′(bpy(OH)2)]2+, and [Ru(bpy)3]2+ (44′(bpy(OH)2 = 4,4′-dihydroxy-2,2′-bipyridine) in HeLa cells, which have a relatively low pH. It is found that [Ru(bpy)2(66′(bpy(OH)2)]2+ is more cytotoxic than the other ruthenium complexes studied. Thus, we have identified a pH sensitive ruthenium scaffold that can be exploited for photo-induced anti-cancer activity.

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Section: Methodsmentioning

confidence: 99%

Ruthenium dihydroxybipyridine complexes are tumor activated prodrugs due to low pH and blue light induced ligand release

Hufziger

Thowfeik

Charboneau

et al. 2014

Journal of Inorganic Biochemistry

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“…The current MCPs were parameterized using a scalar relativistic wavefunction, but our previous iMCPs [37][38][39] have both non-and scalar relativistic versions, and this would allow us to predict the effect of relativity on bond length and interaction energy. A sample calculation was done with XeAgCl.…”

Section: Resultsmentioning

confidence: 99%

Comparison of xenon and radon metal halides

Lovallo

Kłobukowski

2015

Chemical Physics Letters

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“…Ground-state gas-phase geometry optimization was performed at the Hartree-Fock level of theory (RHF, ROHF and UHF) using the SBKJC, Def2-TZVP, IMCP-NR1 and IMCP-SR1 basis sets. 31,32 The calculations were carried out using the GAMESS-US package 33 for the Def2-TZVP, IMCP-NR1 and IMCP-SR1 basis sets and FireFly version 8.1.1 34 for the SBKJC basic set. The effect of solvent (water) was taken into account in the framework of the polarizable continuum model (PCM).…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Short-lived intermediates in photochemistry of an OsCl62− complex in aqueous solutions

Rogozina

Yudanov

Федунов

et al. 2018

Photochem Photobiol Sci

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Two mechanisms of OsCl photolysis were studied by means of quantum chemical calculations in gas and aqueous phases. The difference between these mechanisms is in the nature of the possible Os(iv) key intermediates (KI). According to calculations, the intermediate is an OsCl complex of square pyramidal coordination geometry. The calculations do not give an opportunity to make an unambiguous choice between the triplet and quintet multiplicities of OsCl. The calculated CASSCF/IMCP-SR1 transition energies for OsCl are lower than for OsCl, while the calculated XMC-QDPT2/SBKJC spectra for the triplet state are in better agreement with the experimental absorption spectrum of the KI than for the quintet state.

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Improved model core potentials for the second‐ and third‐row transition metals

Cited by 29 publications

References 43 publications

Ruthenium dihydroxybipyridine complexes are tumor activated prodrugs due to low pH and blue light induced ligand release

Ruthenium dihydroxybipyridine complexes are tumor activated prodrugs due to low pH and blue light induced ligand release

Comparison of xenon and radon metal halides

Short-lived intermediates in photochemistry of an OsCl62− complex in aqueous solutions

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