Cp*Fe II - - PowerPoint PPT Presentation

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Cp*Fe II - - PowerPoint PPT Presentation

Jan 09, 2024 277 likes •390 views

3R1-17 Cp*Fe II CATALYTIC HYDROGENATION WITH A BIFUNCTIONAL

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SLIDE 1

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

3R1-17

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SLIDE 2

nucleophilic hydride electrophilic proton δ - δ + δ - δ + Ru N H H H C O R' R P Ph2 a possible transition state

CATALYTIC HYDROGENATION WITH A BIFUNCTIONAL Ru CATALYST

A B A B H H 18e amine complex 16e amido complex base precursor Ru N H Ru N H H H = ketone, epoxide, imide, α,β–unsaturated carbonyl catalyst H2 P Ph2 P Ph2 A B Ru N N H H CMe + Chloro complex Nitrile complex Ru N Cl H H P P Ph2 Ph2 catalyst precursor

  • Org. Biomol. Chem. 2006, 4, 393-406.
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SLIDE 3

Fe Ru Os

4 5 6 VIII

Ru complex Ru N L H H P Ph2 Fe complex Fe N L H H P Ph2

DESIGN OF NOVEL Cp*Fe(PN) COMPLEXES

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SLIDE 4

PPh2 NH2 = NH2 PPh2 NH2 PPh2 NH2 PPh2 a b c

SYNTHESIS OF [Cp*Fe(P–NH2)(CO)]+ COMPLEXES

toluene reflux, 24 h + Fe CO N P Ph2 H2 I Fe CO OC I PPh2 NH2 1 1a : 73% yield b : 90% yield c : 87% yield

P21/a (#14) R1 = 0.047 wR2 = 0.119

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SLIDE 5

COMPARISON WITH [Cp*Fe(P –NH2)(CO)]+ COMPLEXES

Fe CO N P Ph2 H2 I IR (KBr) : νC≡O cm-1 1928 80.3 1922 54.2 H2N PPh2 PPh2 H2N

31P NMR (CD2Cl2, δ, ppm)

1945 75.4 H2N PPh2 83.8(1) 91.2(1) bite angle (° ) 83.07(6) Fe CO N P Ph2 H2 + Ru CO N P Ph2 H2 + IR (KBr) : νC≡O cm-1

31P NMR (CD2Cl2, δ, ppm)

80.3 64.5 1941 1948 The 84th Annual Meetings of CSJ, 2004. 52nd Symp. Organomet. Chem. Jpn. 2005.

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SLIDE 6

hν Oxidant

SYNTHESIS OF CO

–FREE [Cp*Fe(P –NH2)L]+ COMPLEX Fe CO N P Ph2 H2 + Fe O O Fe Cl N N Me2 Me2 x Ph2P NH2 Fe L N P Ph2 H2 +

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SLIDE 7

SYNTHESIS OF CO

–FREE [Cp*Fe(P –NH2)L]+ COMPLEX Fe CO N P Ph2 H2 + Fe O O Fe Cl N N Me2 Me2 x hν Oxidant Ph2P NH2 unsuitable precursors no reaction complicated

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SLIDE 8

P1 (#2) R1 = 0.041 wR2 = 0.093

SYNTHESIS OF CO–FREE [Cp*Fe(P–NH2)(MeCN)]+ COMPLEX

Ru NCMe N P Ph2 H2 + Fe NCMe N P Ph2 H2 +

31P NMR (CD2Cl2, δ, ppm)

82.8 62.6 IR (KBr) : νC≡N cm-1 2264 2249 Fe CO OC I

  • 1. toluene, AlCl3
  • 2. KI / H2O

dark yellow crystal 70% yield hν , MeCN Fe NCMe N P Ph2 H2 I Fe I Ph2P NH2 purple crystal 90% yield

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SLIDE 9

O H Fe cat, t-C4H9OK 2-propanol, 70 °C, 13 h S/C = 20 [ketone] = 0.5 M in 2-propanol OH + H2 20 atm Ru NCMe N P Ph2 H2 + Fe NCMe N P Ph2 H2 93% yield + (determined by GC) Fe cat = Fe CO N P Ph2 H2 + <1% yield 94% yield (3 h)

CATALYTIC HYDROGENATION WITH Cp*Fe(P–NH2) COMPLEX

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SLIDE 10

toluene, reflux SYNTHESIS OF Cp*Fe COMPLEXES BEARING PN LIGANDS Fe CO N P Ph2 H2 I Fe CO OC I CATALYTIC HYDROGENATION WITH [Cp*Fe(P –NH2)(MeCN)]I COMPLEX Fe cat = O H Fe cat, t-C4H9OK 2-propanol, 70 °C, 13 h S/C = 20 [ketone] = 0.5 M in 2-propanol OH 93% yield + H2 20 atm

  • 1. toluene, AlCl3
  • 2. KI / H2O

hν , MeCN Fe NCMe N P Ph2 H2 I Fe I Ph2P NH2

SUMMARY

Fe NCMe N P Ph2 H2 I Ph2P NH2