228704-38-9Relevant articles and documents
Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen-Type Lanthanide (III) Complexes
Berardozzi, Roberto,Pescitelli, Gennaro,Di Pietro, Sebastiano,Resta, Claudio,Ballistreri, Francesco P.,Pappalardo, Andrea,Tomaselli, Gaetano A.,Di Bari, Lorenzo
, p. 857 - 863 (2015)
The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides stable and inert complexes KLnL2 upon simple reaction with lanthanide halides or pseudohalides LnX3 (Ln = Tb3+-Lu3+/sup
Chiral (1,2)-diphenylethylene-salen complexes of triel metals: Coordination patterns and mechanistic considerations in the isoselective ROP of lactide
Maudoux, Nicolas,Roisnel, Thierry,Dorcet, Vincent,Carpentier, Jean-Francois,Sarazin, Yann
, p. 6131 - 6147 (2014)
The synthesis of enantiomerically pure aluminium, gallium and indium complexes supported by chiral (R,R)-(HHONNOHH) (1), (R,R)-(MeHONNOHMe) (2), (R,R)-(tButBuONNO tButBu) (3), (R,R)-(MeNO2ONNOMeNO2) (4), (R,R)-(HOMeONNOHOMe) (5) and (R,R)-( ClClONNOClCl) (6) (1,2)-diphenylethylene-salen ligands is described. Several of these complexes have been crystallographically authenticated, which highlights a diversity of coordination patterns. Whereas all Ga complexes form [Ga2(CH2SiMe3) 4(ONNO)] bimetallic species (ONNO=1-3), aluminium [AlR(ONNO)] (R=Me, CH2SiMe3) and indium [In(CH2SiMe 3)(ONNO)] derivatives are monometallic for ONNO=1, 2 and 4-6, and only form the bimetallic complexes [Al2R4(ONNO)] and [In2(CH2SiMe3)4(ONNO)] for the most sterically crowded ligand 3. The [AlMe(ONNO)] complexes react with iPrOH to give [AlOiPr(ONNO)] complexes that are robust towards further iPrOH. The [In(CH 2SiMe3)(ONNO)] congeners are inert towards excess alcohol, whereas the Ga compounds decompose easily. All these alkyl complexes, as well as the [AlOiPr(ONNO)] derivatives, catalyse the ring-opening polymerisation (ROP) of racemic lactide (rac-LA). The [AlMe(ONNO)] complexes require additional alcohol to afford controlled reactions, but [AlOiPr(ONNO)] complexes are single-component catalysts for the isoselective ROP of rac-LA, with values of Pm in the range 0.80-0.90. Experimental evidence unexpectedly shows that chain-end control leads to the isoselectivity of these aluminium catalysts; also, the more crowded the coordination sphere, the higher the isoselectivity. The bimetallic Ga complexes do not afford controlled reactions, but the binary [In(ONNO)(CH2SiMe3)/(PhCH2OH)] systems competently mediate non-stereoselective ROP; evidence is given that an activated monomer mechanism is at work. Kinetic studies show that catalytic activity decreases when electronic density and steric congestion at the metal atom increase. Class act: A new range of monometallic chiral salen-aluminium complexes based on a less-classical chiral backbone has been developed. These constitute efficient precatalysts for the isoselective ring-opening polymerisation of racemic lactide. According to chain-end control, they afford poly(lactide) (PLA) featuring high isotacticity (Pm≈0.80-0.90) in the upper range reported to date (see figure).
Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R, R)-1,2-Diphenylethylenediamine
Emelyanov, Mikhail A.,Stoletova, Nadezhda V.,Smol'Yakov, Alexander F.,Il'In, Mikhail M.,Maleev, Victor I.,Larionov, Vladimir A.
supporting information, p. 13960 - 13967 (2021/09/11)
Here we report the first synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (R,R)-1,2-diphenylethylenediamine and salicylaldehyde. Both diastereoisomers with opposite chiralities at the metal center (Λ and Δconfigurations) were prepared. The new Co(III) complexes possessed both acidic hydrogen-bond donating (HBD) NH moieties and nucleophilic counteranions and operate as bifunctional chiral catalysts for the challenging kinetic resolution of terminal and disubstituted epoxides by the reaction with CO2 under mild conditions. The highest selectivity factor (s) of 2.8 for the trans-chalcone epoxide was achieved at low catalyst loading (2 mol %) in chlorobenzene, which is the best achieved result currently for this type of substrate.
Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand
Cui, Long,Lv, Zhong-Peng,Leong, Chanel F.,Ru, Jing,D'Alessandro, Deanna M.,You, Song,Zuo, Jing-Lin
, p. 16575 - 16584 (2016/11/06)
The π-conjugated tetrathiafulvalene (TTF) annulated ligand was introduced into a dicyanometallate for the first time, leading to the synthesis of the versatile redox-active dicyanideferrite building block [(n-Bu)4N][Fe(TTFbp)(CN)2] (