0000000000355027
AUTHOR
Armand Soldera
Generation, Characterization, and Electrochemical Behavior of the Palladium-Hydride Cluster [Pd3(dppm)3(3-CO)(3-H)]+ (dppm=Bis(diphenylphosphinomethane)
Addition of formate on the dicationic cluster [Pd(3)(dppm)(3)(mu(3)-CO)](2+) (dppm=bis(diphenylphosphinomethane) affords quantitatively the hydride cluster [Pd(3)(dppm)(3)(mu(3)-CO)(mu(3)-H)](+). This new palladium-hydride cluster has been characterised by (1)H NMR, (31)P NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry. The unambiguous identification of the capping hydride was made from (2)H NMR spectroscopy by using DCO(2) (-) as starting material. The mechanism of the hydride complex formation was investigated by UV/Vis stopped-flow methods. The kinetic data are consistent with a two-step process involving: 1) host-guest interactions between HCO(2) (-) and [Pd(3)(dppm)(3)(mu(3…
Luminescent P-Chirogenic Copper Clusters
P-chirogenic clusters of the cubanes [Cu4I4L4] (L = chiral phosphine) were prepared from (+)- and (-)-ephedrine with L = (S)- or (R)-(R)(Ph)(i-Pr)P (with R = CH3 (seven steps) or C17H35 (10 steps)) with e.e. up to 96%. The X-ray structure of [Cu4I4((R)-(CH3)(Ph)(i-Pr)P)4] confirmed the cubane structure with average Cu···Cu and Cu···I distances of 2.954 and 2.696 Å, respectively. The cubane structure of the corresponding [Cu4I4((S)-(CH3)(Ph)(i-Pr)P)4] was established by the comparison of the X-ray powder diffraction patterns, and the opposite optical activity of the (S)- and (R)-ligand-containing clusters was confirmed by circular dichroism spectroscopy. Small-angle X-ray scattering patterns…
Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines through Azomethine Ylide Cycloaddition Reaction.
A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused pip…
ChemInform Abstract: Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines Through Azomethine Ylide Cycloaddition Reaction.
A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused pip…
Unexpected Reaction of the Unsaturated Cluster Host and Catalyst [Pd3(3-CO)(dppm)3]2+ with the Hydroxide Ion: Spectroscopic and Kinetic Evidence of an Inner-Sphere Mechanism
The title cluster, [Pd(3)(mu(3)-CO)(dppm)(3)](2+) (dppm=bis(diphenylphosphino)methane), reacts with one equivalent of hydroxide anions (OH(-)), from tetrabutylammonium hydroxide (Bu(4)NOH), to give the paramagnetic [Pd(3)(mu(3)-CO)(dppm)(3)](+) species. Reaction with another equivalent of OH(-) leads to the zero-valent compound [Pd(3)(mu(3)-CO)(dppm)(3)](0). From electron paramagnetic resonance analysis of the reaction medium using the spin-trap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the 2-tetrahydrofuryl or methyl radicals, deriving from the tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) solvent, respectively, were detected. For both [Pd(3)(mu(3)-CO)(dppm)(3)](2+) and [Pd(3)(mu…
CCDC 1405446: Experimental Crystal Structure Determination
Related Article: Saoussen Haddad, Sarra Boudriga, François Porzio, Armand Soldera, Moheddine Askri, Michael Knorr, Yoann Rousselin, Marek M. Kubicki, Christopher Golz, and Carsten Strohmann|2015|J.Org.Chem.|80|9064|doi:10.1021/acs.joc.5b01399
CCDC 1405448: Experimental Crystal Structure Determination
Related Article: Saoussen Haddad, Sarra Boudriga, François Porzio, Armand Soldera, Moheddine Askri, Michael Knorr, Yoann Rousselin, Marek M. Kubicki, Christopher Golz, and Carsten Strohmann|2015|J.Org.Chem.|80|9064|doi:10.1021/acs.joc.5b01399
CCDC 1405449: Experimental Crystal Structure Determination
Related Article: Saoussen Haddad, Sarra Boudriga, François Porzio, Armand Soldera, Moheddine Askri, Michael Knorr, Yoann Rousselin, Marek M. Kubicki, Christopher Golz, and Carsten Strohmann|2015|J.Org.Chem.|80|9064|doi:10.1021/acs.joc.5b01399
CCDC 1424523: Experimental Crystal Structure Determination
Related Article: Antony Lapprand, Mathieu Dutartre, Naïma Khiri, Etienne Levert, Daniel Fortin, Yoann Rousselin, Armand Soldera, Sylvain Jugé and Pierre D. Harvey|2013|Inorg.Chem.|52|7958|doi:10.1021/ic400498j
CCDC 1405447: Experimental Crystal Structure Determination
Related Article: Saoussen Haddad, Sarra Boudriga, François Porzio, Armand Soldera, Moheddine Askri, Michael Knorr, Yoann Rousselin, Marek M. Kubicki, Christopher Golz, and Carsten Strohmann|2015|J.Org.Chem.|80|9064|doi:10.1021/acs.joc.5b01399