About: Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes

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Description	Rhodium(III) and iridium(III) octahedral complexes of general formula [MCl3{R2PCH2C(But)=NN=C(But)CH2PR2}] (M = Rh, Ir; R = Ph, c-C6H11, Pri, But) were prepared either from the corresponding diphosphinoazines and RhCl3 3H2O or by oxidation of previously reported bridging complexes [{MCl(1,2-h:5,6-h-CH=CHCH2CH2CH=CHCH2CH2 )}2{m-R2PCH2C(But)=NN= C(But) CH2R2}] with chlorine-containing solvents. Depending on steric properties of the ligands, complexes with facial or meridional configuration were obtained. Crystal and molecular structures of four complexes were determined by X-ray diffraction. Hemilability of ligand in the complex fac-[RhCl3{(C6H11)2PCH2C(But)=NN=C(But)CH2P(C6H11)2}] consisting in reversible decoordination of the phosphine donor group in the six-membered ring was observed. Variable temperature 31P NMR measurement and subsequent simulation gave a value of concentration of the partially decoordinated species about 1 mol % and a rate of exchange approximately 100 s-1. Rhodium(III) and iridium(III) octahedral complexes of general formula [MCl3{R2PCH2C(But)=NN=C(But)CH2PR2}] (M = Rh, Ir; R = Ph, c-C6H11, Pri, But) were prepared either from the corresponding diphosphinoazines and RhCl3 3H2O or by oxidation of previously reported bridging complexes [{MCl(1,2-h:5,6-h-CH=CHCH2CH2CH=CHCH2CH2 )}2{m-R2PCH2C(But)=NN= C(But) CH2R2}] with chlorine-containing solvents. Depending on steric properties of the ligands, complexes with facial or meridional configuration were obtained. Crystal and molecular structures of four complexes were determined by X-ray diffraction. Hemilability of ligand in the complex fac-[RhCl3{(C6H11)2PCH2C(But)=NN=C(But)CH2P(C6H11)2}] consisting in reversible decoordination of the phosphine donor group in the six-membered ring was observed. Variable temperature 31P NMR measurement and subsequent simulation gave a value of concentration of the partially decoordinated species about 1 mol % and a rate of exchange approximately 100 s-1. (en)
Title	Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes (en)
skos:prefLabel	Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes (en)
skos:notation	RIV/67985858:_____/09:00335772!RIV10-MSM-67985858
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(GA203/01/0554), P(GA203/06/0738), P(LC06070), Z(AV0Z40720504), Z(MSM0021620857)
http://linked.open...iv/cisloPeriodika	1
http://linked.open...vai/riv/dodaniDat	2010
http://linked.open...aciTvurceVysledku	Čermák, Jan Sýkora, Jan Pošta, Martin
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 chemických procesů AV ČR, v. v. i.
http://linked.open...dnocenehoVysledku	310632
http://linked.open...ai/riv/idVysledku	RIV/67985858:_____/09:00335772
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	polydentate ligands; diphosphinoazines; hemilabile ligands (en)
http://linked.open.../riv/klicoveSlovo	hemilabile ligands polydentate ligands diphosphinoazines
http://linked.open...odStatuVydavatele	NL - Nizozemsko
http://linked.open...ontrolniKodProRIV	[4C316BE18582]
http://linked.open...i/riv/nazevZdroje	Inorganica chimica acta
http://linked.open...in/vavai/riv/obor	CA
http://linked.open...ichTvurcuVysledku	3 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Advanced techniques for 29Si NMR spectroscopy The structure and synthetic applications of transition metal complexes New highly active catalysts for the Heck reaction
http://linked.open...UplatneniVysledku	2009
http://linked.open...v/svazekPeriodika	362
http://linked.open...iv/tvurceVysledku	Sýkora, Jan Čermák, Jan Pošta, Martin Vojtíšek, P. Cisařová, I.
http://linked.open...ain/vavai/riv/wos	000261274400030
http://linked.open...n/vavai/riv/zamer	Investigation of multiphase reacting systems for the design of processes important in synthesis and preparation of novel materials, in energy production and in environmental protection Nové molekulární systémy pro pokročilé aplikace prospěšné pro zdraví a šetrné k životnímu prostředí
issn	0020-1693
number of pages	9 (xsd:int)
is http://linked.open...avai/riv/vysledek of	Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes Diphosphinoazine Rhodium(III) and Iridium(III) Octahedral Complexes

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