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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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