Dataset Information

Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7- Backbone.

ABSTRACT: Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4- (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4- (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3- for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4- (Ru-N3); (ii) [PW11O39{RuIII(N4HC-CH3)}]4- (Ru-Tz) as a click-reaction product; and (iii) [PW11O39{RuII(N2)}]5- (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.

SUBMITTER: Mukhacheva AA

PROVIDER: S-EPMC7221517 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7- Backbone.

Mukhacheva Anna A AA Gushchin Artem L AL Yanshole Vadim V VV Abramov Pavel A PA Sokolov Maksim N MN

Molecules (Basel, Switzerland) 20200417 8

Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4- (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4- (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3- for CH3CN in the presence of an NaN ...[more]

PMID: 32316614

Similar Datasets

Project description:The factor inhibiting HIF (FIH) is a proximate oxygen sensor for human cells, hydroxylating Asn(803) within the ?-subunit of the hypoxia inducible factor (HIF). FIH is an ?-ketoglutatrate (?KG)-dependent, non-heme Fe(II) dioxygenase, in which Fe(II) is coordinated by a (His(2)Asp) facial triad, ?KG, and H(2)O. Hydrogen bonding among the facial triad, the HIF-Asn(803) side chain, and various second-sphere residues suggests a functional role for the second coordination sphere in tuning the chemistry of the Fe(II) center. Point mutants of FIH were prepared to test the functional role of the ?KG-centered (Asn(205) and Asn(294)) or HIF-Asn(803)-centered (Arg(238) and Gln(239)) second-sphere residues. The second sphere was tested for local effects on priming Fe(II) to react with O(2), oxidative decarboxylation, and substrate positioning. Steady-sate kinetics were used to test for overall catalytic effects; autohydroxylation rates were used to test for priming and positioning, and electronic spectroscopy was used to assess the primary coordination sphere and the electrophilicity of ?KG. Asn(205) ? Ala and Asn(294) ? Ala mutants exhibited diminished rates of steady-state turnover, while minimally affecting autohydroxylation, consistent with impaired oxidative decarboxylation. Blue-shifted metal to ligand charge transfer transitions for (Fe+?KG)FIH indicated that these point mutations destabilized the ?* orbitals of ?KG, further supporting a slowed rate of oxidative decarboxylation. The Arg(238) ? Met mutant exhibited steady-state rates too low to measure and diminished product yields, suggesting impaired substrate positioning or priming; the Arg(238) ? Met mutant was capable of O(2) activation for the autohydroxylation reaction. The Gln(239) ? Asn mutant exhibited significantly slowed steady-state kinetics and diminished product yields, suggesting impaired substrate positioning or priming. As HIF binding to the Gln(239) ? Asn mutant stimulated autohydroxylation, it is more likely that this point mutant simply mispositions the HIF-Asn(803) side chain. This work combines kinetics and spectroscopy to show that these second-sphere hydrogen bonds play roles in promoting oxidative decarboxylation, priming Fe(II) to bind O(2), and positioning HIF-Asn(803).

Dataset Information

Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7- Backbone.

Publications

Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW<sub>11</sub>O<sub>39</sub>]<sup>7-</sup> Backbone.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets