About: Singlet Diradical Complexes of Chromium, Molybdenum, and Tungsten with Azo Anion Radical Ligands from M(CO)6 Precursors     Goto   Sponge   NotDistinct   Permalink

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Description
  • The homoleptic diamagnetic complexes M(mer-L)2, M = Cr, Mo,W (1a,b, 2a,b, and 4a,b), were obtained by reacting the hexacarbonyls M(CO)6 with the tridentate ligands 2-[(2-N-arylamino)phenylazo]pyridine (HL = NH4C5N=NC6H4N(H)C6H4(H) (HLa) or NH4C5N=NC6H4N(H)C6H4(CH3) (HLb)) in refluxing n-octane. In the case of M = Mo, the dinuclear compounds [Mo(L)(pap)]2(-O) (3a,b) (pap = 2-(phenylazo)pyridine), were obtained as second products in moist solvent. X-ray diffraction analysis for Cr(Lb)2 (1b), Mo(La)2 (2a), and W(La)2 (4a) reveals considerably distorted-octahedral structures with trans-positioned azo-N atoms and cis-positioned 2-pyridyl-N and anilido nitrogen atoms. Whereas the Nazo-M-Nazo angle is larger than 170, the other two trans angles are smaller, at about 155 (M = Cr, 1b) or 146 (M = Mo, W; 2a, 4a), due to the overarching bite of the mer-tridentate ligands.
  • The homoleptic diamagnetic complexes M(mer-L)2, M = Cr, Mo,W (1a,b, 2a,b, and 4a,b), were obtained by reacting the hexacarbonyls M(CO)6 with the tridentate ligands 2-[(2-N-arylamino)phenylazo]pyridine (HL = NH4C5N=NC6H4N(H)C6H4(H) (HLa) or NH4C5N=NC6H4N(H)C6H4(CH3) (HLb)) in refluxing n-octane. In the case of M = Mo, the dinuclear compounds [Mo(L)(pap)]2(-O) (3a,b) (pap = 2-(phenylazo)pyridine), were obtained as second products in moist solvent. X-ray diffraction analysis for Cr(Lb)2 (1b), Mo(La)2 (2a), and W(La)2 (4a) reveals considerably distorted-octahedral structures with trans-positioned azo-N atoms and cis-positioned 2-pyridyl-N and anilido nitrogen atoms. Whereas the Nazo-M-Nazo angle is larger than 170, the other two trans angles are smaller, at about 155 (M = Cr, 1b) or 146 (M = Mo, W; 2a, 4a), due to the overarching bite of the mer-tridentate ligands. (en)
  • Byly připraveny homoleptické diamagnetické komplexy M(mer-L)2, M = Cr, Mo or W. Rentgenostrukturní analýza pro Cr(Lb)2 (1b), Mo(La)2 (2a) a W(La)2 (4a) ukázala na výrazně porušenou octaedrickou strukturu těchto komplexů. Vazebné vzdálenosti N-N jsou v rozmezí 1.339(2) A (1b) až 1.373(3) A (4a), tento fakt zřetelně indikuje přítomnost azo radikálového aniontu. Všechny sloučeniny mohou být reversilně redukovány. Diamagnetism těchto komplexů určený pomocí měření magnetické susceptibility a 1H NMR experimentu vyplývá ze spin-spinové interakce mezi azo skupinami v trans polohách. Tato interakce též vede k singletnímu diradikálovému stavu. Elektronová struktura těchto singletních systémů byla počítána DFT metodou používající přístup porušené symetrie v spinově neomezeném přiblížení. Experimentální struktury a fyzikální vlastosti byly velice dobře popsány kvantově chemickými výpočty. (cs)
Title
  • Singlet Diradical Complexes of Chromium, Molybdenum, and Tungsten with Azo Anion Radical Ligands from M(CO)6 Precursors
  • Singlet Diradical Complexes of Chromium, Molybdenum, and Tungsten with Azo Anion Radical Ligands from M(CO)6 Precursors (en)
  • Singletní diradikálové komplexy chromia, molybdenu a wolframu s azo anionovými radikálovými ligandy připravené z M(CO)6 precursorů (cs)
skos:prefLabel
  • Singlet Diradical Complexes of Chromium, Molybdenum, and Tungsten with Azo Anion Radical Ligands from M(CO)6 Precursors
  • Singlet Diradical Complexes of Chromium, Molybdenum, and Tungsten with Azo Anion Radical Ligands from M(CO)6 Precursors (en)
  • Singletní diradikálové komplexy chromia, molybdenu a wolframu s azo anionovými radikálovými ligandy připravené z M(CO)6 precursorů (cs)
skos:notation
  • RIV/61388955:_____/07:00093600!RIV08-MSM-61388955
http://linked.open.../vavai/riv/strany
  • 8584;8593
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • P(GA203/03/0822), P(OC 139), P(OC D15.10), R, Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika
  • 21
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 450049
http://linked.open...ai/riv/idVysledku
  • RIV/61388955:_____/07:00093600
http://linked.open...riv/jazykVysledku
http://linked.open.../riv/klicovaSlova
  • singlet diradical complexes; chromium; molybdenum; tungsten (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • US - Spojené státy americké
http://linked.open...ontrolniKodProRIV
  • [3018AB0ECD40]
http://linked.open...i/riv/nazevZdroje
  • Inorganic Chemistry
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
http://linked.open...cetTvurcuVysledku
http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 46
http://linked.open...iv/tvurceVysledku
  • Fiedler, Jan
  • Kaim, W.
  • Sarkar, B.
  • Záliš, Stanislav
  • Chatterjee, S.
  • Singh, P.
  • Goswami, S.
  • Castineiras, A.
  • Sanyal, A.
http://linked.open...n/vavai/riv/zamer
issn
  • 0020-1669
number of pages
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