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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 1
JKCSEZ 37(1)
February 20, 1993 

 
Title
Synthesis and Reactions of Organoruthenium(Ⅲ) Complexes

새로운 3가 유기루테늄 착물의 합성과 반응
Author
Dong-Hwan Lee, Hag-Gu Kim, Dae-Ryong Seo, Byung-Soon Kim

이동환, 김학구, 서대룡, 김병순
Keywords
Abstract
[(η5-C5Me5)RuCl2]2 (1)과 1당량의 포스핀을 반응시켜 새로운 상자기성 루테늄(Ⅲ) 착물 (η5-C5Me5)RuCl2(PR3) (PR3 = PMe3, PEt3, PiPr3, PCy3, PMe2Ph, PMePh2, PPh3, P(p-C6H4CH3)3, DPPE, DPPB, Py) (2a∼2k)를 합성하였다. 자기화율의 측정으로 부터 얻어진 착물 (2a∼2k)의 유효자기모멘트값(μeff = 1.65∼2.07 B.M.)은 분자내 짝을 이루지 않는 전자가 1개 있는 전자배치의 경우와 일치하였다. 디클로로루테늄(Ⅲ) 착물 (η5-C5Me5)RuCl2(PR3) (2) 는 (ⅰ)아세톤 용매 중에서 KBr과 반응하여 디브로모루테늄(Ⅲ) 착물 (η5-C5Me5)RuBr2(PR3) (PR3 = PPh3)로 전환되었고, (ⅱ) 디에틸에테르 용매 중에서 Na/Hg과 반응하여 비스(포스핀) 유도체 (η5-C5Me5)RuCl(PR3)2 (PR3 = PMe3, PMePh2)로 환원되었으며, (iii) CO와 반응하여 카르보닐 유도체(η5-C5Me5)RuCl(PR3)(CO) (PR3 = PMe3, PPh3)를 생성하였다.

The paramagnetic organoruthenium(Ⅲ) complexes (η5-C5Me5)RuCl2(PR3) (PR3 = PMe3, PEt3, PiPr3, PCy3, PMe2Ph, PMePh2, PPh3, P(p-C6H4CH3)3, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of [(η5-C5Me5)RuCl2]2 (1) with 1 equivalent of the corresponding phosphines (PR3). The effective magnetic moment (μeff = 1.65∼2.07 B.M.) derived from the magnetic susceptibility measurements of the complexes (2a∼2k) were consistent with the presence of a "single" unpaired electron in the molecule. Treatment of dichlororuthenium (Ⅲ) complex (η5-C5Me5)RuCl2(PR3) (2) (ⅰ) with KBr in acetone afforded the dibromoruthenium (Ⅲ) complex (η5-C5Me5)RuBr2(PR3) (PR3 = PPh3), (ⅱ) with sodium amalgam in diethylether led to the bis(phosphine) derivatives (η5-C5Me5)RuCl(PR3)2 (PR3 = PMe3, PMePh2), and (ⅲ) with carbonmonoxide gave to the carbonyl derivatives (η5-C5Me5)RuCl(PR3)(CO) (PR3 = PMe3, PPh3).

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