Title

製備不同位置具拉電子基之高立障含鈷單牙磷基及其鈀金屬錯合物並應用於Amination和Suzuki 耦合反應

Translated Titles

Preparations of Cobalt-containing Bulky Monodentate Phosphines with Trifluoromethyl Substituents on Arylethyne and Their Applications in Amination and Suzuki Reactions

DOI

10.6845/NCHU.2008.01066

Authors

黃柏誠

Key Words

耦合催化反應 ; 含雙鈷金屬單牙磷基 ; Amination reaction ; Suzuki-Miyaura cross-coupling reaction ; Ortho-metallation ; Phosphine ligand ; Transmetallation ; Electron-Withdrawing Substituent

PublicationName

中興大學化學系所學位論文

Volume or Term/Year and Month of Publication

2008年

Academic Degree Category

碩士

Advisor

洪豐裕

Content Language

繁體中文

Chinese Abstract

中文摘要 合成一系列具強拉電子基之高立障含鈷單牙磷基(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-(tBu)2PC≡C(Ar)) (4cm: Ar=3-CF3C6H4; 4cmm: Ar=3,5-(CF3)2C6H3)。並利用4cmm進行Amination耦合反應。其中,改變可能影響催化效果之因素例如:鈀金屬與配位基比例、鹼、溶劑、鈀金屬種類等,並討論其結果。 使用4cm與Pd(OAc)2合成具有單一磷配位基配位的鈀金屬錯合物(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-(tBu)2PC≡C(Ar)-κC1)Pd(μ-OAc), ( 5cm: Ar=3-CF3C6H4),5cm之晶體結構由單晶繞射法鑑定得之。發現在結構中有ortho-metallation現象產生。 再更進一步利用4cmm與Pd(COD)Cl2合成具有單一磷位基配位的鈀金屬錯合物{[(μ-PPh2CH2PPh2)Co2(CO)4] [(μ,η-(tBu)2PC≡CAr)]PdCl2}( 6cmm: Ar=3,5-(CF3)2C6H3),6cmm之晶體結構由單晶繞射法鑑定出。其結構呈現出鈀與鈷金屬之間具有直接金屬-金屬鍵的架構。 利用所合成一系列的催化劑(4cm/[Pd]、4cmm/[Pd]、5cm、6cmm)進行Amination及Suzuki耦合反應,都有不錯的效果。強拉電子基-CF3的確對反應速度的加快有助益。

English Abstract

Abstract Several cobalt-containing bulky monodentate phosphines (μ-PPh2CH2PPh2)Co2(CO)4(μ,η-(tBu)2PC≡C(Ar)) (4cm: Ar=3-CF3C6H4; 4cmm: Ar=3,5-(CF3)2C6H3) were prepared from the reactions of ((tBu)2PC≡C(Ar)) (2cm: Ar=3-CF3C6H4; 2cmm: Ar=3,5-(CF3)2C6H3) with Co2(CO)6(μ-PPh2CH2PPh2) 3. Further reaction of 4cm with Pd(OAc)2 yielded a unique palladium complex (μ-PPh2CH2PPh2) Co2(CO)4(μ,η-(tBu)2PC≡C(Ar)- κC1)Pd(μ-OAc), ( 5cm: Ar=3-CF3C6H4). Reaction of 4cmm with Pd(COD)Cl2 yielded a unique palladium complex {[(μ-PPh2CH2PPh2)Co2(CO)4][(μ,η-(tBu)2PC≡CAr)] PdCl2}, ( 6cmm: Ar=3,5-CF3C6H3). The strong electron-withdrawing substituent -CF3, assists the ortho-metallation process during the formation of 5cm or 6cmm. The enhancement of the reaction rates of the Amination and Suzuki-Miyaura cross-coupling reactions using 5cm and 6cmm are thereby attributed to this effect.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系所
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