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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 4
JKCSEZ 37(4)
August 20, 1993 

Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(Ⅱ) Theoretical Studies on Palladium(0, Ⅱ) Complexes of Unsaturated Carboxylic Acids

포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 2 보). 불포화카르복실산이 배위된 팔라듐 (0, Ⅱ) 착물에 관한 이론적 연구
Myung-Ki Doh, Bong-Gon Kim, Maeng-Jun Jung, Young-Dae Song, Byung-Kak Park

도명기, 김봉곤, 정맹준, 송영대, 박병각
Acrylic acid, methacrylic acid, crotonic acid(A 그룹), 또는 3-butenoic acid 4-pentenoic acid(B group) 등이 배위된 bis(trimethylphosphine) 팔라듐(O) 착물에서 π-및 metallacycle의 안정한 구조와 반응성을 분자역학법과 확장분자궤도함수법으로 조사하였다. 올레핀의 HOMO 및 LUMO 계수가 큰 A 그룹 리간드는 π-착물이 안정화되고, LUMO 계수가 상대적으로 적은 B 그룹 리간드는 금속함유고리화합물이 안정하였으며, 특히, 3-butenoic acid에서는 6원고리 화합물보다 메틸기를 갖는 5원고리 화합물이 더 안정함을 알 수 있었다.

The structure and reactivity of π-and metallacycle form in the bis(trimethylphosphine) palladium(0) complexes with acrylic acid, methacrylic acid, crotonic acid(A group) and 3-butenoic acid, 4-pentenoic acid(B group) have been investigated by Molecular Mechanics and Extended Huckel Molecular Orbital method. The calculation shows that A groups with large value of frontier electron density of HOMO and LUMO produce π-complexes instead of metallacycle. But B groups with small value of frontier electron density of LUMO, especially 3-butenoic acid, form stable metallacycle. Moreover the methyl-substituted five-membered compared with the six-membered metallacycle is energetically stable conformation.

431 - 441
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