Synthesis, characterization and structural systematics in diorganotin complexes with O,N,O' tris-chelating semirigid diaza-scaffolds: Mono- vs. di-nuclear Compounds

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18470%2F20%3A50017240" target="_blank" >RIV/62690094:18470/20:50017240 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/abs/pii/S0022328X20304253" target="_blank" >https://www.sciencedirect.com/science/article/abs/pii/S0022328X20304253</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jorganchem.2020.121522" target="_blank" >10.1016/j.jorganchem.2020.121522</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis, characterization and structural systematics in diorganotin complexes with O,N,O' tris-chelating semirigid diaza-scaffolds: Mono- vs. di-nuclear Compounds

Popis výsledku v původním jazyce

A series of nine novel diorganotin(IV) complexes of O,N,O&apos; chelating ligands were synthesized viz., [n-Bu2Sn(L-2)](2)center dot 0.25(C6H14) (1), [Me2Sn(L-1)](2)center dot(C7H8) (2), [n-Bu2Sn(L-1)](2)center dot(C7H8) (3), [Me2Sn(L-3)](2)center dot(C7H8) (4), 2 [n-Bu2Sn(L-3)](2)center dot 4 (n-Bu2Sn(L-3)) (5), [Ph2Sn(L-3)] (6), [Ph2Sn(L-1)] (7), [Ph2Sn(L-4)] (8) and [Ph2Sn(L-2)] (9) and structurally characterized. The ligand scaffolds differ with respect to the chemical link between the coordinating N and O atoms, which is either an alkyl or an aryl moiety. Diffraction results indicate that the smallest methyl groups favor dimerization via Sn-O-Sn bridging and six-coordination at the cation. Among these dinuclear derivatives, more asymmetric oxygen bridges and longer Sn center dot center dot center dot Sn separations are found for the less nucleophilic phenolate O. In contrast, the bulky phenyl substituents prevent aggregation for both classes of ligands and always lead to five-coordinated mononuclear species. The n-Bu groups are sterically more demanding than Me but flexible, resulting in an intermediate behavior. When the O,N,O&apos; ligand with phenolate O coordinates a Sn(n-Bu)(2) fragment, a borderline situation occurs and both mono- and dinuclear complexes coexist in the same crystalline solid. The overall structural variety is reflected in a range of different Addison-tau(5) [Addison et al., J. Chem. Soc., Dalton Trans. 1984, 1349-1356] descriptors for five-fold coordination. For better comparability we introduce a slightly modified geometry index tau&apos;(5), in which the basal angle alpha is subtended by the organic substituents, regardless of its absolute value. tau&apos;(5) represents a sensitive indicator for the coordination geometry about Sn-IV. Tin NMR results revealed that all compounds exist as mononuclear pentacoordinated species in solution. (c) 2020 Elsevier B.V. All rights reserved.

Název v anglickém jazyce

Synthesis, characterization and structural systematics in diorganotin complexes with O,N,O' tris-chelating semirigid diaza-scaffolds: Mono- vs. di-nuclear Compounds

Popis výsledku anglicky

A series of nine novel diorganotin(IV) complexes of O,N,O&apos; chelating ligands were synthesized viz., [n-Bu2Sn(L-2)](2)center dot 0.25(C6H14) (1), [Me2Sn(L-1)](2)center dot(C7H8) (2), [n-Bu2Sn(L-1)](2)center dot(C7H8) (3), [Me2Sn(L-3)](2)center dot(C7H8) (4), 2 [n-Bu2Sn(L-3)](2)center dot 4 (n-Bu2Sn(L-3)) (5), [Ph2Sn(L-3)] (6), [Ph2Sn(L-1)] (7), [Ph2Sn(L-4)] (8) and [Ph2Sn(L-2)] (9) and structurally characterized. The ligand scaffolds differ with respect to the chemical link between the coordinating N and O atoms, which is either an alkyl or an aryl moiety. Diffraction results indicate that the smallest methyl groups favor dimerization via Sn-O-Sn bridging and six-coordination at the cation. Among these dinuclear derivatives, more asymmetric oxygen bridges and longer Sn center dot center dot center dot Sn separations are found for the less nucleophilic phenolate O. In contrast, the bulky phenyl substituents prevent aggregation for both classes of ligands and always lead to five-coordinated mononuclear species. The n-Bu groups are sterically more demanding than Me but flexible, resulting in an intermediate behavior. When the O,N,O&apos; ligand with phenolate O coordinates a Sn(n-Bu)(2) fragment, a borderline situation occurs and both mono- and dinuclear complexes coexist in the same crystalline solid. The overall structural variety is reflected in a range of different Addison-tau(5) [Addison et al., J. Chem. Soc., Dalton Trans. 1984, 1349-1356] descriptors for five-fold coordination. For better comparability we introduce a slightly modified geometry index tau&apos;(5), in which the basal angle alpha is subtended by the organic substituents, regardless of its absolute value. tau&apos;(5) represents a sensitive indicator for the coordination geometry about Sn-IV. Tin NMR results revealed that all compounds exist as mononuclear pentacoordinated species in solution. (c) 2020 Elsevier B.V. All rights reserved.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of organometallic chemistry

ISSN

0022-328X

e-ISSN

—

Svazek periodika

927

Číslo periodika v rámci svazku

November

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

11

Strana od-do

"Article Number: 121522"

Kód UT WoS článku

000579416000011

EID výsledku v databázi Scopus

2-s2.0-85091078860