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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F03%3A54030062%21RIV%2F2004%2FAV0%2FA54004%2FN
rdf:type
n9:Vysledek skos:Concept
dcterms:description
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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 -system of the allenylidene ligand are decoupled resulting in a significantly longer CN bond. 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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 -system of the allenylidene ligand are decoupled resulting in a significantly longer CN bond.
dcterms:title
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. 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.
skos:prefLabel
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. 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.
skos:notation
RIV/61388955:_____/03:54030062!RIV/2004/AV0/A54004/N
n3:strany
2342;2352
n3:aktivita
n4:P n4:Z
n3:aktivity
P(OC D15.10), Z(AV0Z4040901)
n3:cisloPeriodika
N/A
n3:dodaniDat
n5:2004
n3:domaciTvurceVysledku
n6:3953084
n3:druhVysledku
n7:J
n3:duvernostUdaju
n18:S
n3:entitaPredkladatele
n13:predkladatel
n3:idSjednocenehoVysledku
597892
n3:idVysledku
RIV/61388955:_____/03:54030062
n3:jazykVysledku
n12:eng
n3:klicovaSlova
aminoallenylidene complexes; ruthenium; experimental study
n3:klicoveSlovo
n8:experimental%20study n8:aminoallenylidene%20complexes n8:ruthenium
n3:kodStatuVydavatele
GB - Spojené království Velké Británie a Severního Irska
n3:kontrolniKodProRIV
[3856A24D3868]
n3:nazevZdroje
Journal of the Chemical Society. Dalton Transactions
n3:obor
n14:CF
n3:pocetDomacichTvurcuVysledku
1
n3:pocetTvurcuVysledku
4
n3:pocetUcastnikuAkce
0
n3:pocetZahranicnichUcastnikuAkce
0
n3:projekt
n15:OC%20D15.10
n3:rokUplatneniVysledku
n5:2003
n3:svazekPeriodika
N/A
n3:tvurceVysledku
Winter, R. F. Záliš, Stanislav Klinkhammer, K. W. Hartmann, S.
n3:zamer
n16:AV0Z4040901
s:issn
1472-7773
s:numberOfPages
11