S–H Bond cleavage versus thiol co-ordination in half-sandwich ruthenium complexes †

1999 ◽  
pp. 4309-4314 ◽  
Author(s):  
Alberto Coto ◽  
Isaac de los Ríos ◽  
Manuel Jiménez Tenorio ◽  
M. Carmen Puerta ◽  
Pedro Valerga
Keyword(s):  
Bond Cleavage ◽  
Ruthenium Complexes ◽  
Half Sandwich

scholarly journals New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2′-Bis(aminomethyl)-1,1′-binaphthyl

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1165
Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya
Keyword(s):  
Hydrogen Transfer ◽  
Bond Cleavage ◽  
Enantiomeric Excess ◽  
Transfer Hydrogenation ◽  
Catalyst Precursor ◽  
Asymmetric Catalysts ◽  
Axially Chiral ◽  
Diastereomeric Mixture ◽  
Raney Ni ◽  
Half Sandwich

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2′-bis(aminomethyl)-1,1′-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = η5–C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.

ChemInform Abstract: Half-Sandwich Arene Ruthenium Complexes: Synthetic Strategies and Relevance in Catalysis

ChemInform ◽  
2014 ◽  
Vol 45 (15) ◽  
pp. no-no
Author(s):  
Prashant Kumar ◽  
Rakesh Kumar Gupta ◽  
Daya Shankar Pandey
Keyword(s):  
Ruthenium Complexes ◽  
Half Sandwich

Selective Bond Cleavage Reactions by Low-Valent Ruthenium Complexes

ChemInform ◽  
2003 ◽  
Vol 34 (18) ◽  
Author(s):  
Masafumi Hirano ◽  
Nobuyuki Komine ◽  
Sanshiro Komiya
Keyword(s):  
Bond Cleavage ◽  
Ruthenium Complexes ◽  
Cleavage Reactions ◽  
Low Valent

Rhodamine-modified fluorescent half-sandwich iridium and ruthenium complexes: potential application as bioimaging and anticancer agents

2019 ◽  
Vol 48 (15) ◽  
pp. 4788-4793 ◽  
Author(s):  
Wenli Ma ◽  
Lihua Guo ◽  
Zhenzhen Tian ◽  
Shumiao Zhang ◽  
Xiangdong He ◽  
...  
Keyword(s):  
Mechanism Of Action ◽  
Anticancer Agents ◽  
Potential Application ◽  
Ruthenium Complexes ◽  
Anticancer Complexes ◽  
Half Sandwich

Most half-sandwich metal anticancer complexes are non-fluorescent, which results in an uncertain mechanism of action (MoA).

Optically Active Ortho-Metalated Half-Sandwich Ruthenium Complexes:  Solid-State NMR as a Convenient Tool To Analyze Mixtures of Diastereomers

2001 ◽  
Vol 40 (20) ◽  
pp. 5117-5122 ◽  
Author(s):  
Vincent Ritleng ◽  
Philippe Bertani ◽  
Michel Pfeffer ◽  
Claude Sirlin ◽  
Jérôme Hirschinger
Keyword(s):  
Solid State ◽  
Solid State Nmr ◽  
Ruthenium Complexes ◽  
Optically Active ◽  
Convenient Tool ◽  
Half Sandwich

Activation of Alkynols by Half-Sandwich Ruthenium Complexes:  Isolation of Hydroxyalkynyl(hydrido) and Hydroxyvinylidene Derivatives

1999 ◽  
Vol 18 (6) ◽  
pp. 950-951 ◽  
Author(s):  
Emilio Bustelo ◽  
Manuel Jiménez-Tenorio ◽  
M. Carmen Puerta ◽  
Pedro Valerga
Keyword(s):  
Ruthenium Complexes ◽  
Half Sandwich

Cationic 16-electron half-sandwich ruthenium complexes containing asymmetric diamines: understanding the stability and reactivity of coordinatively unsaturated two-legged piano stool complexes

1999 ◽  
Vol 286 (1) ◽  
pp. 114-120 ◽  
Author(s):  
Christian Gemel ◽  
Valentin N. Sapunov ◽  
Kurt Mereiter ◽  
Mathias Ferencic ◽  
Roland Schmid ◽  
...  
Keyword(s):  
Ruthenium Complexes ◽  
The Stability ◽  
Half Sandwich
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