About: Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB).

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About: Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB). Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	The reactions of [fac-Re(CO)3(bpy)(MeOH)](PF6) with the TCNX ligands (TCNE, TCNQ, TCNB) in CH2Cl2 gave very different results. No reaction was observed with TCNB (1,2,4,5-tetracyanobenzene) whereas TCNE produced very labile intermediates which converted under mild conditions to structurally characterized {(-CN)[fac-Re(CO)3(bpy)]2}(PF6) with an eclipsed conformation relative to the Re-CN-Re axis. With TCNQ a stable tetranuclear complex {(4-TCNQ)[Re(CO)3(bpy)]4}(BF4)4 was obtained. Its structural, electrochemical and spectroscopic analysis indicates only negligible charge transfer from the rhenium(I) centers to the extremely strong  acceptor TCNQ. DFT calculations were used to confirm and explain the absence of electron delocalization from the metals to the TCNQ bridge. Correspondingly, the X-band and high-frequency (285 GHz) EPR data well as the IR and UV/VIS/NIR spectroelectrochemical results support the almost total confinement of the added electron. The reactions of [fac-Re(CO)3(bpy)(MeOH)](PF6) with the TCNX ligands (TCNE, TCNQ, TCNB) in CH2Cl2 gave very different results. No reaction was observed with TCNB (1,2,4,5-tetracyanobenzene) whereas TCNE produced very labile intermediates which converted under mild conditions to structurally characterized {(-CN)[fac-Re(CO)3(bpy)]2}(PF6) with an eclipsed conformation relative to the Re-CN-Re axis. With TCNQ a stable tetranuclear complex {(4-TCNQ)[Re(CO)3(bpy)]4}(BF4)4 was obtained. Its structural, electrochemical and spectroscopic analysis indicates only negligible charge transfer from the rhenium(I) centers to the extremely strong  acceptor TCNQ. DFT calculations were used to confirm and explain the absence of electron delocalization from the metals to the TCNQ bridge. Correspondingly, the X-band and high-frequency (285 GHz) EPR data well as the IR and UV/VIS/NIR spectroelectrochemical results support the almost total confinement of the added electron. (en)
Title	Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB). Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB). (en)
skos:prefLabel	Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB). Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB). (en)
skos:notation	RIV/61388955:_____/03:54030214!RIV/2004/AV0/A54004/N
http://linked.open.../vavai/riv/strany	7018;7025
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(OC D14.20), P(OC D15.10), Z(AV0Z4040901)
http://linked.open...iv/cisloPeriodika	22
http://linked.open...vai/riv/dodaniDat	2004
http://linked.open...aciTvurceVysledku	Fiedler, Jan Záliš, Stanislav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	623844
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/03:54030214
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	magnetic-properties; coordination chemistry; radical complex (en)
http://linked.open.../riv/klicoveSlovo	magnetic-properties coordination chemistry radical complex
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[C8E4EF9F0730]
http://linked.open...i/riv/nazevZdroje	Inorganic Chemistry
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	8 (xsd:int)
http://linked.open...ocetUcastnikuAkce	0 (xsd:int)
http://linked.open...nichUcastnikuAkce	0 (xsd:int)
http://linked.open...vavai/riv/projekt	http://linked.opendata.cz/resource/domain/vavai/projekt/OC%20D14.20 http://linked.opendata.cz/resource/domain/vavai/projekt/OC%20D15.10
http://linked.open...UplatneniVysledku	2003
http://linked.open...v/svazekPeriodika	42
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Kaim, W. Záliš, Stanislav Klein, A. Frantz, S. Wanner, M. Hartmann, H. Duboc-Toia, C.
http://linked.open...n/vavai/riv/zamer	Objasňování zákonitostí vztahů struktury a vlastností - zejména dynamiky a chemické reaktivity - látek a molekulárních systémů
issn	0020-1669
number of pages	8 (xsd:int)

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