Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release
Authors
Sovari, Sara NasiriKolly, Isabelle
Schindler, Kevin
Cortat, Youri
Liu, Shing-Chi
Crochet, Aurelien
Pavić, Aleksandar
Zobi, Fabio
Article (Published version)
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The reaction of rhenium alpha-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)(2)(NO)(N-N)X](+) species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)(2)(NO)(N-N)X](+) is that of a hard Re acid, probably due to the stronger pi-acceptor properties of NO+ as compared to those of CO. The metal ion thus shows great affinity for pi-basic ligands, which are consequently difficult to replace by, e.g., sigma-donor or weak pi-acids like pyridine. Attempts of direct nitrosylation of alpha-diimine fac-[Re(CO)(3)](+) complexes bearing pi-basic OR-type ligands gave the [Re(CO)(2)(NO)(N-N)(BF4)][BF4] salt as the onl...y product in good yield, featuring a stable Re-FBF3 bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)(2)(NO)(N-N)X](+) complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs.
Keywords:
rhenium / photoCORM / nitrosyl / dicarbonylSource:
Molecules, 2021, 26, 17Publisher:
- MDPI, Basel
Funding / projects:
- Fonds de recherche du Centenaire de l'Universite de Fribourg [818]
- Swiss National Science Foundation [200021_196967]
DOI: 10.3390/molecules26175302
ISSN: 1420-3049
PubMed: 34500734
WoS: 000694265500001
Scopus: 2-s2.0-85114189610
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Institution/Community
Institut za molekularnu genetiku i genetičko inženjerstvoTY - JOUR AU - Sovari, Sara Nasiri AU - Kolly, Isabelle AU - Schindler, Kevin AU - Cortat, Youri AU - Liu, Shing-Chi AU - Crochet, Aurelien AU - Pavić, Aleksandar AU - Zobi, Fabio PY - 2021 UR - https://imagine.imgge.bg.ac.rs/handle/123456789/1459 AB - The reaction of rhenium alpha-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)(2)(NO)(N-N)X](+) species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)(2)(NO)(N-N)X](+) is that of a hard Re acid, probably due to the stronger pi-acceptor properties of NO+ as compared to those of CO. The metal ion thus shows great affinity for pi-basic ligands, which are consequently difficult to replace by, e.g., sigma-donor or weak pi-acids like pyridine. Attempts of direct nitrosylation of alpha-diimine fac-[Re(CO)(3)](+) complexes bearing pi-basic OR-type ligands gave the [Re(CO)(2)(NO)(N-N)(BF4)][BF4] salt as the only product in good yield, featuring a stable Re-FBF3 bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)(2)(NO)(N-N)X](+) complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs. PB - MDPI, Basel T2 - Molecules T1 - Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release IS - 17 VL - 26 DO - 10.3390/molecules26175302 ER -
@article{ author = "Sovari, Sara Nasiri and Kolly, Isabelle and Schindler, Kevin and Cortat, Youri and Liu, Shing-Chi and Crochet, Aurelien and Pavić, Aleksandar and Zobi, Fabio", year = "2021", abstract = "The reaction of rhenium alpha-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)(2)(NO)(N-N)X](+) species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)(2)(NO)(N-N)X](+) is that of a hard Re acid, probably due to the stronger pi-acceptor properties of NO+ as compared to those of CO. The metal ion thus shows great affinity for pi-basic ligands, which are consequently difficult to replace by, e.g., sigma-donor or weak pi-acids like pyridine. Attempts of direct nitrosylation of alpha-diimine fac-[Re(CO)(3)](+) complexes bearing pi-basic OR-type ligands gave the [Re(CO)(2)(NO)(N-N)(BF4)][BF4] salt as the only product in good yield, featuring a stable Re-FBF3 bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)(2)(NO)(N-N)X](+) complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs.", publisher = "MDPI, Basel", journal = "Molecules", title = "Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release", number = "17", volume = "26", doi = "10.3390/molecules26175302" }
Sovari, S. N., Kolly, I., Schindler, K., Cortat, Y., Liu, S., Crochet, A., Pavić, A.,& Zobi, F.. (2021). Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release. in Molecules MDPI, Basel., 26(17). https://doi.org/10.3390/molecules26175302
Sovari SN, Kolly I, Schindler K, Cortat Y, Liu S, Crochet A, Pavić A, Zobi F. Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release. in Molecules. 2021;26(17). doi:10.3390/molecules26175302 .
Sovari, Sara Nasiri, Kolly, Isabelle, Schindler, Kevin, Cortat, Youri, Liu, Shing-Chi, Crochet, Aurelien, Pavić, Aleksandar, Zobi, Fabio, "Efficient Direct Nitrosylation of alpha-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release" in Molecules, 26, no. 17 (2021), https://doi.org/10.3390/molecules26175302 . .