Solution structures and behavior of trans-RuH(eta(1)-BH(4)) (binap)(1,2-diamine) complexes

The solution structures of a number of trans-RuH(eta(1)-BH(4))[(S)-tolbinap](1,2-diamine) precatalysts [TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; 1,2-diamine==(S,S)- or (R,R)-1,2-diphenylethylenediamine (DPEN), ethylenediamine (EN), and (S)-1,1-di(4-anisyl)-2-isopropylethyl...

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Veröffentlicht in:Magnetic resonance in chemistry : MRC. - 1985. - 44(2006), 1 vom: 01. Jan., Seite 66-75
1. Verfasser: Sandoval, Christian A (VerfasserIn)
Weitere Verfasser: Yamaguchi, Yoshiki, Ohkuma, Takeshi, Kato, Koichi, Noyori, Ryoji
Format: Aufsatz
Sprache:English
Veröffentlicht: 2006
Zugriff auf das übergeordnete Werk:Magnetic resonance in chemistry : MRC
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Amines BINAP, 2-naphthol Ligands Naphthalenes Organometallic Compounds Solutions Ruthenium 7UI0TKC3U5
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245 1 0 |a Solution structures and behavior of trans-RuH(eta(1)-BH(4)) (binap)(1,2-diamine) complexes 
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500 |a Date Revised 21.11.2013 
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520 |a The solution structures of a number of trans-RuH(eta(1)-BH(4))[(S)-tolbinap](1,2-diamine) precatalysts [TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; 1,2-diamine==(S,S)- or (R,R)-1,2-diphenylethylenediamine (DPEN), ethylenediamine (EN), and (S)-1,1-di(4-anisyl)-2-isopropylethylenediamine (DAIPEN)] have been determined using 2D NMR ((1)H--(1)H DQF-COSY, (1)H--(13)C HMQC, (1)H--(31)P HSQC, and (1)H--(15)N HSQC), and a double-pulsed field-gradient spin-echo (DPFGSE) NOE technique. All the octahedral Ru complexes adopt a trans configuration with respect to the BH(4) and hydride ligands. Amine protons of trans-RuH(eta(1)-BH(4))[(S)-tolbinap](1,2-diamine) complexes undergo H/D exchange in (CD(3))(2)CDOD. This inherent high acidity, coupled with the lability and chemical properties of the BH(4) ligand, allows for precatalyst activation without the need for an added base, in contrast to trans-RuCl(2)[(S)-tolbinap](1,2-diamine) precatalysts, which require a strong base for generation of a catalytic species. The H/BH(4) complex in a 2-propanol solution is converted to catalytically active [trans-RuH{(S)-tolbinap}{(S,S)-dpen}(ROH)](+) [(RO)(ROH)(n)](-) (R = (CH(3))(2)CH), a loosely associated ion pair of the discrete (solvated) cationic fragment and anionic species 
650 4 |a Journal Article 
650 4 |a Research Support, Non-U.S. Gov't 
650 7 |a Amines  |2 NLM 
650 7 |a BINAP, 2-naphthol  |2 NLM 
650 7 |a Ligands  |2 NLM 
650 7 |a Naphthalenes  |2 NLM 
650 7 |a Organometallic Compounds  |2 NLM 
650 7 |a Solutions  |2 NLM 
650 7 |a Ruthenium  |2 NLM 
650 7 |a 7UI0TKC3U5  |2 NLM 
700 1 |a Yamaguchi, Yoshiki  |e verfasserin  |4 aut 
700 1 |a Ohkuma, Takeshi  |e verfasserin  |4 aut 
700 1 |a Kato, Koichi  |e verfasserin  |4 aut 
700 1 |a Noyori, Ryoji  |e verfasserin  |4 aut 
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