Platinum-Modified Adenines: Unprecedented Protonation Behavior
Revealed by NMR Spectroscopy and Relativistic
Density-Functional Theory Calculations

J 2012

Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations

VÍCHA, Jan, Gabriel DEMO a Radek MAREK

Základní údaje

Originální název

Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations

Autoři

VÍCHA, Jan (203 Česká republika, domácí), Gabriel DEMO (703 Slovensko, domácí) a Radek MAREK (203 Česká republika, garant, domácí)

Vydání

Inorganic Chemistry, American Chemical Society, 2012, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/ic201595e

Impakt faktor

Impact factor: 4.593

Kód RIV

RIV/00216224:14740/12:00057245

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/ic201595e

UT WoS

000300474700027

Klíčová slova anglicky

Adenine; 15N NMR spectroscopy; Platinum; Relativistic DFT; Spin-orbit; Protonation

Štítky

ok, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 4. 1. 2014 13:38, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

Two novel Pt(IV) complexes of aromatic cytokinins with possible antitumor properties were prepared by reaction of selected aminopurines with K2PtCl6. The structures of both complexes, 9-[6-(benzylamino)purine] pentachloroplatinate (IV) and 9-[6-(furfurylamino)purine] pentachloroplatinate (IV), were characterized in detail by using two-dimensional NMR spectroscopy (1H, 13C, 15N, and 195Pt) in solution and CP/MAS NMR techniques in the solid state. We report for the first time the X-ray structure of a nucleobase adenine derivative coordinated to Pt(IV) via the N9 atom. The protonation equilibria for the complexes in solution were characterized by using NMR spectroscopy (isotropic chemical shifts and indirect nuclear spin–spin coupling constants) and the structural conclusions drawn from the NMR analysis are supported by relativistic density-functional theory (DFT) calculations. Because of the presence of the Pt atom, hybrid GGA functionals and scalar-relativistic and spin–orbit corrections were employed for both the DFT calculations of the molecular structure and particularly for the NMR chemical shifts. In particular, the populations of the N7-protonated and neutral forms of the complexes in solution were characterized by correlating the experimental and the DFT-calculated NMR chemical shifts. In contrast to the chemical exchange process involving the N7–H group, the hydrogen atom at N3 was determined to be unexpectedly rigid, probably because of the presence of the stabilizing intramolecular interaction N3-H...Cl. The described methodology combining the NMR spectroscopy and relativistic DFT calculations can be employed for characterizing the tautomeric and protonation equilibria in a large family of transition-metal-modified purine bases.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

GAP206/11/0550, projekt VaV

Název: NMR spektroskopie pevného stavu organických molekul, polymorfů, solvátů a komplexů (Akronym: ssNMR)

Investor: Grantová agentura ČR, NMR spektroskopie pevného stavu organických molekul, polymorfů, solvátů a komplexů

GAP206/12/0539, projekt VaV

Název: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy (Akronym: METALIN)

Investor: Grantová agentura ČR, Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy

Přiložené soubory

IC12_51_1371.pdf

Požádat o autorskou verzi souboru

Citovat

VÍCHA, Jan, Gabriel DEMO a Radek MAREK. Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations. Inorganic Chemistry. American Chemical Society, 2012, roč. 51, č. 3, s. 1371-1379. ISSN 0020-1669. Dostupné z: https://dx.doi.org/10.1021/ic201595e.

@article{967092,
   author = {Vícha, Jan and Demo, Gabriel and Marek, Radek},
   article_number = {3},
   doi = {http://dx.doi.org/10.1021/ic201595e},
   keywords = {Adenine; 15N NMR spectroscopy; Platinum; Relativistic DFT; Spin-orbit; Protonation},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations},
   url = {http://dx.doi.org/10.1021/ic201595e},
   volume = {51},
   year = {2012}
}

TY  - JOUR
ID  - 967092
AU  - Vícha, Jan - Demo, Gabriel - Marek, Radek
PY  - 2012
TI  - Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations
JF  - Inorganic Chemistry
VL  - 51
IS  - 3
SP  - 1371-1379
EP  - 1371-1379
PB  - American Chemical Society
SN  - 00201669
KW  - Adenine
KW  - 15N NMR spectroscopy
KW  - Platinum
KW  - Relativistic DFT
KW  - Spin-orbit
KW  - Protonation
UR  - http://dx.doi.org/10.1021/ic201595e
L2  - http://dx.doi.org/10.1021/ic201595e
N2  - Two novel Pt(IV) complexes of aromatic cytokinins with possible antitumor properties were prepared by reaction of selected aminopurines with K2PtCl6. The structures of both complexes, 9-[6-(benzylamino)purine] pentachloroplatinate (IV) and 9-[6-(furfurylamino)purine] pentachloroplatinate (IV), were characterized in detail by using two-dimensional NMR spectroscopy (1H, 13C, 15N, and 195Pt) in solution and CP/MAS NMR techniques in the solid state. We report for the first time the X-ray structure of a nucleobase adenine derivative coordinated to Pt(IV) via the N9 atom. The protonation equilibria for the complexes in solution were characterized by using NMR spectroscopy (isotropic chemical shifts and indirect nuclear spin–spin coupling constants) and the structural conclusions drawn from the NMR analysis are supported by relativistic density-functional theory (DFT) calculations. Because of the presence of the Pt atom, hybrid GGA functionals and scalar-relativistic and spin–orbit corrections were employed for both the DFT calculations of the molecular structure and particularly for the NMR chemical shifts. In particular, the populations of the N7-protonated and neutral forms of the complexes in solution were characterized by correlating the experimental and the DFT-calculated NMR chemical shifts. In contrast to the chemical exchange process involving the N7–H group, the hydrogen atom at N3 was determined to be unexpectedly rigid, probably because of the presence of the stabilizing intramolecular interaction N3-H...Cl. The described methodology combining the NMR spectroscopy and relativistic DFT calculations can be employed for characterizing the tautomeric and protonation equilibria in a large family of transition-metal-modified purine bases.
ER  -

VÍCHA, Jan, Gabriel DEMO a Radek MAREK. Platinum-Modified Adenines: Unprecedented Protonation Behavior Revealed by NMR Spectroscopy and Relativistic Density-Functional Theory Calculations. \textit{Inorganic Chemistry}. American Chemical Society, 2012, roč.~51, č.~3, s.~1371-1379. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/ic201595e.

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