기관회원 [로그인]
소속기관에서 받은 아이디, 비밀번호를 입력해 주세요.
개인회원 [로그인]

비회원 구매시 입력하신 핸드폰번호를 입력해 주세요.
본인 인증 후 구매내역을 확인하실 수 있습니다.

회원가입
서지반출
Kinetics and Mechanism of Alkaline Hydrolysis of [(Methoxy)(p-substituted styryl)-carbene] Pentacarbonyl Chromium(0) Complexes in Aqueous Acetonitrile
[STEP1]서지반출 형식 선택
파일형식
@
서지도구
SNS
기타
[STEP2]서지반출 정보 선택
  • 제목
  • URL
돌아가기
확인
취소
  • Kinetics and Mechanism of Alkaline Hydrolysis of [(Methoxy)(p-substituted styryl)-carbene] Pentacarbonyl Chromium(0) Complexes in Aqueous Acetonitrile
  • Kinetics and Mechanism of Alkaline Hydrolysis of [(Methoxy)(p-substituted styryl)-carbene] Pentacarbonyl Chromium(0) Complexes in Aqueous Acetonitrile
저자명
Shin. Gap-Cheol,Hwang. Jae-Young,Yang. Ki-Yull,Koo. In-Sun,Lee. Ik-Choon
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2005년|26권 12호|pp.1981-1985 (5 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
PDF텍스트
주제분야
기타
이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $ ho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $ ho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${Delta}S^ eq$ value determined in the present system is consistent with the proposed mechanism.