Cp*Fe II - PowerPoint PPT Presentation

3R1-17 一級アミ ン－三級ホスフ ィ ンキレート 配位子を有 する Cp*Fe （ II ） 錯体の合成 （ 東工大院理工） 伊藤 正人○山口 健太郎・ 碇屋 隆雄

CATALYTIC HYDROGENATION WITH A BIFUNCTIONAL Ru CATALYST H 2 base catalyst Ru Ru precursor H Ph 2 P Ph 2 P N H N H H H H A B A B 16e amido complex 18e amine complex = ketone, epoxide, imide, α , β – unsaturated carbonyl A B nucleophilic + hydride R δ + δ - Ru Ru Ru C R' H P Ph 2 P Cl Ph 2 P N CMe Ph 2 N N N O H H H δ - H H H δ + electrophilic Chloro complex Nitrile complex proton catalyst precursor a possible transition state Org. Biomol. Chem. 2006, 4, 393-406.

DESIGN OF NOVEL Cp*Fe(PN) COMPLEXES VIII Fe 4 Ru Fe Ph 2 P L Ph 2 P L N N Ru H H 5 H H Ru complex Fe complex Os 6

SYNTHESIS OF [Cp*Fe(P–NH 2 )(CO)] + COMPLEXES I Ph 2 PPh 2 I P 1a : 73% yield toluene + Fe Fe b : 90% yield reflux, 24 h OC N c : 87% yield CO CO NH 2 H 2 1 PPh 2 PPh 2 PPh 2 PPh 2 = NH 2 NH 2 NH 2 NH 2 a b c P 2 1 / a (#14) R 1 = 0.047 wR 2 = 0.119

–NH 2 )(CO)] + COMPLEXES COMPARISON WITH [Cp*Fe(P H 2 N PPh 2 H 2 N PPh 2 H 2 N PPh 2 I bite angle ( ° ) 83.07(6) 83.8(1) 91.2(1) Ph 2 P IR (KBr) : ν C ≡ O cm -1 1945 1928 1922 Fe 31 P NMR (CD 2 Cl 2 , δ , ppm) 75.4 80.3 54.2 N CO H 2 + + Ph 2 Ph 2 P P Fe Ru N N CO CO H 2 H 2 IR (KBr) : ν C ≡ O cm -1 1941 1948 31 P NMR (CD 2 Cl 2 , δ , ppm) 80.3 64.5 The 84th Annual Meetings of CSJ, 2004 . 52nd Symp. Organomet. Chem. Jpn. 2005 .

– NH 2 )L] + COMPLEX SYNTHESIS OF CO – FREE [Cp*Fe(P + h ν Ph 2 P Oxidant Fe + N CO H 2 Ph 2 P Fe N L NH 2 Me 2 O H 2 Ph 2 P N Fe Fe O N Cl x Me 2

– NH 2 )L] + COMPLEX SYNTHESIS OF CO – FREE [Cp*Fe(P + h ν Ph 2 P Oxidant no reaction Fe N CO H 2 NH 2 Me 2 O Ph 2 P N Fe complicated Fe O N Cl x Me 2 unsuitable precursors

SYNTHESIS OF CO – FREE [Cp*Fe(P – NH 2 )(MeCN)] + COMPLEX I I NH 2 Ph 2 I Ph 2 P 1. toluene, AlCl 3 P Fe Fe h ν , MeCN Fe 2. KI / H 2 O OC CO N NCMe H 2 dark yellow crystal purple crystal 70% yield 90% yield + + Ph 2 Ph 2 P P Ru Fe N N NCMe NCMe H 2 H 2 IR (KBr) : ν C ≡ N cm -1 2249 2264 31 P NMR (CD 2 Cl 2 , δ , ppm ) 82.8 62.6 P 1 (#2) R 1 = 0.041 wR 2 = 0.093

CATALYTIC HYDROGENATION WITH Cp*Fe(P–NH 2 ) COMPLEX O H OH Fe cat, t- C 4 H 9 OK + H 2 2-propanol, 70 °C, 13 h 20 atm S/C = 20 [ketone] = 0.5 M in 2-propanol + + + Ph 2 Ph 2 Fe cat = Ph 2 P P P Fe Ru Fe N N N CO NCMe NCMe H 2 H 2 H 2 <1% yield 93% yield 94% yield (3 h) (determined by GC)

SUMMARY SYNTHESIS OF Cp*Fe COMPLEXES BEARING PN LIGANDS I Ph 2 Ph 2 P NH 2 P Fe toluene, reflux N CO H 2 I Fe I I OC CO NH 2 Ph 2 Ph 2 P 1. toluene, AlCl 3 P Fe Fe h ν , MeCN 2. KI / H 2 O N NCMe H 2 CATALYTIC HYDROGENATION WITH [Cp*Fe(P –NH 2 )(MeCN)]I COMPLEX O I H OH Ph 2 Fe cat, t- C 4 H 9 OK P + H 2 Fe cat = Fe 2-propanol, 70 °C, 13 h 20 atm N NCMe H 2 93% yield S/C = 20 [ketone] = 0.5 M in 2-propanol