Search results for "isocyanide"
showing 10 items of 34 documents
Azole-containing cationic bis-cyclometallated iridium(iii) isocyanide complexes: a theoretical insight into the emission energy and emission efficien…
2019
Using a density functional theory approach, we explore the emission properties of a family of bis-cyclometallated cationic iridium(iii) complexes of general formula [Ir(C^N)2(CN-tert-Bu)2]+ that have tert-butyl isocyanides as neutral auxiliary ligands. Taking the [Ir(ppy)2(CN-tert-Bu)2]+ complex (Hppy = 2-phenylpyridine) as a reference, the effect of replacing the pyridine ring in the cyclometallating ppy ligand by a five-membered azole ring has been examined. To this end, two series of complexes differing by the nature of the atom (either nitrogen or carbon) linking the azole to the phenyl ring of the cyclometallating ligand have been designed. Each series is composed of three molecules ha…
Reaction between Indazole and Pd-Bound Isocyanides-A Theoretical Mechanistic Study
2018
The mechanism of the addition of indazole (Ind)&mdash
A Germanium Isocyanide Complex Featuring (n -> π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C–H Bond Activation under Mild Co…
2012
Reaction of the diarylgermylene Ge(Ar(Me(6)))(2) [Ar(Me(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(CH(3))(3))(2)] with tert-butyl isocyanide gave the Lewis adduct species (Ar(Me(6)))(2)GeCNBu(t), in which the isocyanide ligand displays a decreased C-N stretching frequency consistent with an n → π* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge-C bonding combination between the lone pair of electrons on the germanium atom and the C-N π* orbital of the isocyanide ligand. The complex undergoes facile C-H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu(t) bond.
Mechanism of aminocarbene formation by nucleophilic attack on isocyanide ligands in platinum(II)2-pyrazyl and 4-pyridyl complexes
1997
Abstract The reactions of 2-pyrazyl and 4-pyridyl isocyanide complexes [Pt(CNC 6 H 11 )(C 4 H 3 N 2 - C 2 )(dppe)ClO 4 and [Pt(CNC 6 H 11 )(C 5 H 4 N- C 4 ) (dppe)]ClO 4 ( 1 ) with amines involving the formation of aminocarbene derivatives have been studied kinetically in 1,2-dichloroethane by UV—VIS techniques. The kinetics obey the simple second-order rate law rate = k 2 [ 1 ][amine]. Low activation enthalpies and highly negative activation entropies for the k 2 term are observed. A mechanism is proposed involving direct nucleophilic attack of the amine on the isocyanide carbon with concomitant proton transfer from the amine to the isocyanide nitrogen assisted by the heterocyclic nitrogen…
Reversible complexation of ethylene by a silylene under ambient conditions.
2014
Treatment of toluene solutions of the silylenes Si(SArMe6)2 (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2, 1) or Si(SArPri4)2 (ArPri4 = C6H3-2,6(C6H3-2,6-Pri2)2, 2) with excess ethylene gas affords the siliranes (ArMe6S)2tiebar above startSiCH2tiebar above endCH2 (3) or (ArPri4S)2tiebar above startSiCH2tiebar above endCH2 (4). Silirane 4 evolves ethylene spontaneously at room temperature in toluene solution. A Van’t Hoff analysis by variable-temperature 1H NMR spectroscopy showed that ΔGassn = −24.9(2.5) kJ mol–1 for 4. A computational study of the reaction mechanism using a model silylene Si(SPh)2 (Ph = C6H5) was in harmony with the Van’t Hoff analysis, yielding ΔGassn = −24 kJ mol–1 and an activatio…
CCDC 952600: Experimental Crystal Structure Determination
2014
Related Article: Jana Leppin, Christoph Förster, and Katja Heinze|2014|Inorg.Chem.|53|1039|doi:10.1021/ic4025102
CCDC 1542913: Experimental Crystal Structure Determination
2017
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1541822: Experimental Crystal Structure Determination
2017
Related Article: Svetlana A. Katkova, Mikhail A. Kinzhalov, Peter M. Tolstoy, Alexander S. Novikov, Vadim P. Boyarskiy, Anastasiia Yu. Ananyan, Pavel V. Gushchin, Matti Haukka, Andrey A. Zolotarev, Alexander Yu. Ivanov, Semen S. Zlotsky, Vadim Yu. Kukushkin|2017|Organometallics|36|4145|doi:10.1021/acs.organomet.7b00569
CCDC 1955600: Experimental Crystal Structure Determination
2020
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070
CCDC 857727: Experimental Crystal Structure Determination
2012
Related Article: N.M.Shavaleev, F.Monti, R.D.Costa, R.Scopelliti, H.Bolink, E.Orti, G.Accorsi, N.Armaroli, E.Baranoff, M.Gratzel, M.K.Nazeeruddin|2012|Inorg.Chem.|51|2263|doi:10.1021/ic202297h