Abstract
The paramagnetic organoruthenium(III) complexes $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1) with 1 equivalent of the corresponding phosphines $(PR_3)$. The effective magnetic moment ((${\mu}_{eff} = 1.65∼2.07 B.M.$)) 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 ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) (i) with KBr in acetone afforded the dibromoruthenium (III) complex $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$, (ii) with sodium amalgam in diethylether led to the bis(phosphine) derivatives $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$, and (iii) with carbonmonoxide gave to the carbonyl derivatives $({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$.
$[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1)과 1당량의 포스핀을 반응시켜 새로운 상자기성 루테늄(Ⅲ) 착물 $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k)를 합성하였다. 자기화율의 측정으로 부터 얻어진 착물 (2a∼2k)의 유효자기모멘트값(${\mu}_{eff} = 1.65∼2.07 B.M.$)은 분자내 짝을 이루지 않는 전자가 1개 있는 전자배치의 경우와 일치하였다. 디클로로루테늄(Ⅲ) 착물 ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) 는 (ⅰ)아세톤 용매 중에서 KBr과 반응하여 디브로모루테늄(Ⅲ) 착물 $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$로 전환되었고, (ⅱ) 디에틸에테르 용매 중에서 Na/Hg과 반응하여 비스(포스핀) 유도체 $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$로 환원되었으며, (iii) CO와 반응하여 카르보닐 유도체$({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$를 생성하였다.