title: Solution structures and behavior of trans-RuH(eta(1)-BH(4)) (binap)(1,2-diamine) complexes.
abstract: 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.
authors.affiliation: Department of Chemistry and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
authors.forename: Christian A
authors.initials: CA
authors.lastname: Sandoval
authors.forename: Yoshiki
authors.initials: Y
authors.lastname: Yamaguchi
authors.forename: Takeshi
authors.initials: T
authors.lastname: Ohkuma
authors.forename: Koichi
authors.initials: K
authors.lastname: Kato
authors.forename: Ryoji
authors.initials: R
authors.lastname: Noyori
mesh_terms: D000588:Amines / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry* / Q000378:metabolism; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism; D012428:Ruthenium / Q000737:chemistry* / Q000378:metabolism; D012996:Solutions / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000588:Amines; C406943:BINAP, 2-naphthol; D008024:Ligands; D009281:Naphthalenes; D009942:Organometallic Compounds; D012996:Solutions; D012428:Ruthenium