Substrate activation by the Wilkinson analogous complex containing η2-chelated and η1 P-bonded (methoxyethyl)dicyclohexylphosphine as a hemilabile ligand

Insertion of CS2 into Iridium–Fluorine Bonds

“…The C24-S1 bond [1.697(12) ] is found to be longer than the C24-S2 bond [1.602(11) ], and the CS 2 moiety is bent [S1-C24-S2 140.4 (7)8] in a similar fashion as reported for other compounds bearing a h 2 -CS 2 ligand at rhodium(I), nickel(0) or palladium(0). [23] In accordance with the computational studies the iridium(I) complex 3 does not react with Et 3 N·3 HF (THF, 12 h,50 8C,Scheme 3) or py·HF (C 6 D 6 , 12 h, 508C). Additionally, the presence of CsF or Et 3 N·3 HF does not have any influence on the reaction rate for the conversion of 1 a with CS 2 .…”

Stoichiometric and Catalytic Reactions of the Polysiloxane‐Bound (Ether‐Phosphine)Rhodium(I) Complex [ClRh(PO)(P ∼ O)] in Interphases

“…[25,28] In the case of the CS, adduct 5a(T0), the 31P{1H} NMR spectrum reveals four doublets with nearly identical 'J(RhP) coupling constants (Experimental Section), which are attributed to four diastereomers. If the two chiral phosphine ligands are taken into account, only two diastereomers are expected.…”

Chloride‐Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins

“…[3] However,t oa chieve high asymmetric induction, rhodium catalysts unavoidably require ac oordinating group next to the C=Cd ouble bond. [9] Previously,wedeveloped chloride-bridged dinuclear iridium complexes that dissociated into the corresponding mononuclear monohydride iridium(III) complexes. [5] Thus,h ydrogenation of simple olefins with high enantioselectivity by chiral rhodium systems has remained challenging, [6] despite the tremendous advances in iridium-catalyzed asymmetric hydrogenation of unfunctionalized olefins.I nt his pioneering work, Pfaltz demonstrated the high catalytic performance of P, N-ligated iridium complexes.…”

“…[4] Such high enantioselectivity was considered ac onsequence of the chelating coordination of substrates.Atypically proposed intermediate in asymmetric hydrogenation of olefinic substrates bearing acoordinating amide group involves,1 )both the C = Cd ouble bond and the coordinating functional group,2 )a dihydride rhodium(III) species generated in situ by the reaction of ar hodium(I) precursor with H 2 . [9] Previously,wedeveloped chloride-bridged dinuclear iridium complexes that dissociated into the corresponding mononuclear monohydride iridium(III) complexes. [2b, 4, 7, 8] Aiming to develop arhodium(III) catalytic system, we focused our attention on monohydride rhodium(III) complexes.O ur research was based on the reported reactivity of ethene inserted into aR h À Hb ond of monohydride rhodium(III) complexes bearing dicyclohexyl(2-methoxyethyl)phosphine.…”

“…[5] Thus,h ydrogenation of simple olefins with high enantioselectivity by chiral rhodium systems has remained challenging, [6] despite the tremendous advances in iridium-catalyzed asymmetric hydrogenation of unfunctionalized olefins.I nt his pioneering work, Pfaltz demonstrated the high catalytic performance of P, N-ligated iridium complexes. [9] Previously,wedeveloped chloride-bridged dinuclear iridium complexes that dissociated into the corresponding mononuclear monohydride iridium(III) complexes. [9] Previously,wedeveloped chloride-bridged dinuclear iridium complexes that dissociated into the corresponding mononuclear monohydride iridium(III) complexes.…”