촉매화학 Organometallic Lab..

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Presentation transcript:

촉매화학 Organometallic Lab.

촉매의 종류 균일 촉매(homogenious) : 반응물과 상이 동등한 것 불균일 촉매(heterogenious) : 반응물과 상이 동등하지 않는 것으로 반응물과 섞이지 않음. Ex) Pt, Ni 등. Organometallic Lab.

자동차의 촉매 자동차의 경우에는 Pt의 불균일 촉매를 사용한다. 이는 오일 안에 들어 있는 S와 N 을 포함하고 있어 SOx와 NOx 로 방출되는 가스를 제거해주기 위함이다. Organometallic Lab.

Pd(PPh3)4 = Pd(0) = PdL4(0) 입체적 장애가 심함 Organometallic Lab.

균일 & 불균일 촉매의 비교 균일 촉매 불균일 촉매 촉매형태 단핵전이금속(가용인 mono 착물) 무기산화물에 담지 된 금속 또는 무기 산화물 열에 대한 안정성 낮음 높음 반응상 액체 기체/고체 반응온도 낮음(200℃ ) 높음(250~550℃ ) 촉매활성 반응의 선택성 촉매의 분리 곤란 용이 반응메카니즘 가정을 세워 알아냄 알기 힘들다 Organometallic Lab.

Pd(OAc)2 Organometallic Lab.

Organometallic Lab. Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

산화수 3 4 5 6 7 8 9 10 Ⅰ 2 Ⅱ 1 Ⅲ Ⅳ

18 전자 규칙 중심금속 전자 수 + 리간드 전자 수 = 18개 Fe(CO)4 Fe(CO)5 Fe(CO)6 Fe 8 e- CO 2X4=8e- 2X5=10e- 2X6=12e- 총 전자 수 16e- 18e- 20e- 존재여부 무 유 Organometallic Lab.

Organometallic Lab.

18 전자 rule M + L = 18 Fe = 8e Cp = 5e x 2 = 10  M + L = 18 e Organometallic Lab.

-allyl = Organometallic Lab.

Ni : 10e- COD : 8e- M + L = 18e- Fe : 8e- CO : 6e- 이중결합: 4e- Organometallic Lab.

Cr : 6e- 6 CO : 12e- M + L = 18e- Fe : 8e- 5 CO: 10e- M + L = 18e- Ni : 10e- 4 CO : 8e- Organometallic Lab.

Fe : 8e- 3CO : 6e- 2 ═ : 4e- M + L =18e- Organometallic Lab.

ML2Cl2 형태 Pd = 10e PPh3 = 2e X 2 = 4e Cl = 1e X 2 = 2e M + L = 16e Zr = 4e Cp = 5e X 2 = 10e Cl = 1e X 2 = 2e Organometallic Lab.

금속 올레핀의  결합 올레핀의  결합과 전이금속의 비어있는 d궤도 함수의 결합 (  d) 금속 올레핀의  결합 올레핀의  결합과 전이금속의 비어있는 d궤도 함수의 결합 (  d) (dxy, dyz, dzx) 전이금속의 d궤도 함수와 올레핀의 *의 결합(dxy  *) : back donation Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Reductive Elimination R.E)의 예 (환원적 이탈반응) Organometallic Lab.

Oxidation addition(O.A)의 예 (산화적 첨가 반응) Organometallic Lab.

Organometallic Lab.

촉매의 기본 작용 Organometallic Lab.

배위(coodination)와 해리(dissociation) Organometallic Lab.

Organometallic Lab.

Hydrocyanation of olefins and dienes Organometallic Lab.

4PN 생성의 예 Organometallic Lab.

Vaska`s catalysis Organometallic Lab.

환원적 이탈반응 Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

 - allyl Organometallic Lab.

Allyl의 종류  - allyl :  - allyl : syn(cis)형 anti(trans)형 Organometallic Lab.

Chelate ligand Bidentate Organometallic Lab.

Enantioselective Organometallic Lab.

Allylic amines Organometallic Lab.

Enamine Organometallic Lab.

수소화가 되는 순서 : 치환기 → Ketone → ring Organometallic Lab.

Olefin의 수소화 반응 Ex) Organometallic Lab.

Ex) Organometallic Lab.

Hydroformylation(Oxo reaction) Organometallic Lab.

Cobalt catalysis Co2(CO)8 + H2  HCo(CO)4 Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

L - Phenylalanine (감미료) DIPAMP (cat) Organometallic Lab.

BINAP Organometallic Lab.

Organometallic Lab.

BINAP의 모방 촉매 DIPAMP DIOP CHIRAPHOS Organometallic Lab.

Organometallic Lab.

Hydrosilylation(규소화 수소반응) Organometallic Lab.

Ziegler catalysis Organometallic Lab.

Organometallic Lab.

의 경우 Organometallic Lab.

의 경우 Organometallic Lab.

Organometallic Lab.

Isotactic polymer Organometallic Lab.

Syndiotactic polymer Organometallic Lab.

Aluminum-catalyzed oligomerization of ethylene Organometallic Lab.

Organometallic Lab.

Diels – Alder reaction Organometallic Lab.

Nitrogen의 alkylcatalysis에 Insertion 되었을 때의 다양한 형태 Organometallic Lab.

 -H Elimination transfer Organometallic Lab.

L – Ni + Organometallic Lab.

Organometallic Lab.

L4Ni  L2Ni Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

- allyl의 응용 Organometallic Lab.

Metallacycle (금속고리 화합물) Organometallic Lab.

Organometallic Lab.

Olefin metathesis Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

초산을 만드는 cycle Organometallic Lab.

Vinyl acetate synthesis Organometallic Lab.

: 소반응들에 의해서 생성이 됨으로써 촉매 반응이 원활하게 적용이 되지 않는다. Organometallic Lab.

C1 Chemistry Green chemistry 라고 하며 공해물질로 생각되는 CO를 제거한다. Organometallic Lab.

Organometallic Lab.

Oxo reaction의 예 Organometallic Lab.

Pd(후기(Late)) : Pd의 d궤도 전자 밀도가 높아 전자간 반발이 심해 불안정하다. 과 의 차이 안정성 : Ti > Pd 금속의 성질 : Ti(전기(Early)) : Ti의 d 궤도의 전자 밀도가 낮아 O에서 Ti이로 전자 제공 Pd(후기(Late)) : Pd의 d궤도 전자 밀도가 높아 전자간 반발이 심해 불안정하다. Organometallic Lab.

(Alkoxide) Organometallic Lab.

Carbonylation Organometallic Lab.

Decarbonylation Organometallic Lab.

Organometallic Lab.

Organometallic Lab.

Double carbonylation Organometallic Lab.

Wacker 법 Organometallic Lab. Organometallic Lab.

Organometallic Lab.

에틸렌의 한쪽이 +가 되면서 H2O나 OH가 공격을 하고 -H-elimination이 일어난다. Organometallic Lab.

Organometallic Lab.

Versatility of Palladium( )-catalyzed Reactions of ethylene Reactants Product H2O CH3CHO H2O, HCl, CuCl2 ClCH2CH2OH H2O, HNO3 O2NOCH2CH2ONO2 HOAc CH2=CHOAc HOAc, LiOAc, CuCl2 ClCH2CH2OAc HOAc, NaOAc, CuCl2 AcOCH2CH2OAc HOAc, NiNO3 HOCH2CH2OAc Organometallic Lab.

Organometallic Lab.

CH2=CH2 + HOAc + ½ O2 → CH2 = CHOAc + H2O Organometallic Lab.

질산이 강산이라서 NO3-가 Pd을 공격해서 생성. -H-elimination은 일어나지 않는다. Organometallic Lab.

Allylic oxidation 이중결합 화합물이 Pd에  - 배위 됨. Methyl쪽에 수소가 떨어짐. Organometallic Lab.

Olefin Epoxidation by hydroxides Epoxy는 접착제의 원료이고, 페놀로 접착제를 씻어준다. Organometallic Lab.

DMSO(dimethyl sulfoxide) Acetone DMSO(dimethyl sulfoxide) DMF H2O2 (hydrogen peroxid) : HClO4, NaClO4, KClO4 처럼 산소를 많이 포함하는 화합물은 위험하므로 냉,암소에 보관 Organometallic Lab.

Organometallic Lab.

Organometallic Lab.