Aminoallenylidene Complexes of Ruthenium(II) from the Regioselective Addition of Secondary Amines to Butatrienylidene Intermediates: A Combined Experimental and Theoretical Study of the Hindered Rotation around the CN-Bond.

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030062" target="_blank" >RIV/61388955:_____/03:54030062 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Aminoallenylidene Complexes of Ruthenium(II) from the Regioselective Addition of Secondary Amines to Butatrienylidene Intermediates: A Combined Experimental and Theoretical Study of the Hindered Rotation around the CN-Bond.

Popis výsledku v původním jazyce

Aminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR'')(CH3)]+ are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru=C=C=C=CH2]+. Unsymmetrically substituted amines give rise to Z/E isomeric mixtures. Dynamic 31P-NMR spectroscopy gave an energy barrier of about 85 kJ/mol T for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2RuůC&#61626;C-C(=NRR'''')(CH3)]+. This is also indicated by the pronounced bond length alternation within the RuC3N-chain as is revealed by X-ray structure analysis of the Z isomer of the (benzylmethyl)methylamine derivative 2d. The issue of NR2 rotation was also addressed by DFT calculations on the trans-[Cl(dhpm)2RuC3{N(CH3)2}(CH3)]+ model complex (dhpm = H2PCH2PH2). Upon rotation around the iminium type CN bond nitrogen lone pair and the &#61552;-system of the allenylidene ligand are decoupled resulting in a significantly longer CN bond.

Název v anglickém jazyce

Aminoallenylidene Complexes of Ruthenium(II) from the Regioselective Addition of Secondary Amines to Butatrienylidene Intermediates: A Combined Experimental and Theoretical Study of the Hindered Rotation around the CN-Bond.

Popis výsledku anglicky

Aminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR'')(CH3)]+ are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru=C=C=C=CH2]+. Unsymmetrically substituted amines give rise to Z/E isomeric mixtures. Dynamic 31P-NMR spectroscopy gave an energy barrier of about 85 kJ/mol T for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2RuůC&#61626;C-C(=NRR'''')(CH3)]+. This is also indicated by the pronounced bond length alternation within the RuC3N-chain as is revealed by X-ray structure analysis of the Z isomer of the (benzylmethyl)methylamine derivative 2d. The issue of NR2 rotation was also addressed by DFT calculations on the trans-[Cl(dhpm)2RuC3{N(CH3)2}(CH3)]+ model complex (dhpm = H2PCH2PH2). Upon rotation around the iminium type CN bond nitrogen lone pair and the &#61552;-system of the allenylidene ligand are decoupled resulting in a significantly longer CN bond.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/OC%20D15.10" target="_blank" >OC D15.10: Elektrochemie nano-struktur na heterogenních mezifázích: tvorba, vlastnosti a reakce přenosu elektronu.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2003

Kód důvěrnosti údajů

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

Název periodika

Journal of the Chemical Society. Dalton Transactions

ISSN

1472-7773

e-ISSN

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Svazek periodika

N/A

Číslo periodika v rámci svazku

N/A

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

2342-2352

Kód UT WoS článku

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EID výsledku v databázi Scopus

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