本論文以低價數以及低配位數的釕金屬錯合物與小分子的活化反應為主要重心。其中，以不同的配基所形成的釕金屬錯合物可以分為兩個部分；第一部分為低價數以及低配位數的釕之雙氮基脒錯合物(Ru[-2-HC(N-2,6-iPr2C6H3)2](6-Ar) (Ar = p-cymene, 4; benzene, 6)與小分子的反應；首先，利用雙氮基脒配基與釕金屬反應可以合成出釕二價的錯合物(Ru[-2-HC(N-2,6-iPr2C6H3)2](6-Ar)Cl (Ar = p-cymene, 3; benzene, 4))。將二價的釕金屬錯合物(3,4)加入鉀石墨(KC8)進行還原反應可以合成出低價數以及低配位數的釕金屬錯合物(4,6)。此外，使用AgOTf (OTf = O3SCF3)與錯合物3反應，可以得到錯合物[Ru[-2-HC(N-2,6-iPr2C6H3)2](6-p-cymene)](OTf) (7)。錯合物4與三甲基矽疊氮化合物反應可以得到錯合物Ru[-2-HC(N-2,6-iPr2C6H3)2](6-p-cymene)(N3) (9)。利用錯合物4與兩當量的一氧化氮反應可以得到錯合物{(-NO)Ru(NO)[-2-HC(N-2,6-iPr2C6H3)2]}2 (10)以及活化碳-氫鍵的錯合物Ru2(-OH)[-2-HC(N-2,6-iPr2C6H3)][-2-HC(N-2,6-iPr2C6H3) (N-2-(1-CH2)CH3CH-6-iPrC6H3)] (11)；而錯合物4通入過量的一氧化氮反應可以得到有機化合物HC(N-2,6-iPr2C6H3)[(NO)N-2,6-iPr2C6H3] (12)。錯合物4與過量的一氧化碳反應可以得到兩個產物，錯合物
{Ru[-2-HC(N-2,6-iPr2C6H3)2C(O)](CO)2}2 (13)以及錯合物{Ru[-2-HC(N-2,6-iPr2C6H3)2C(O)](CO)3}2 (14)。
本論文第二部分研究雙和的釕金屬錯合物[(-NO)Ru(Nacnac)]2 (15)與氰化物的反應性。錯合物15與苯氰反應可以生成錯合物Ru(Nacnac)Dipp(NO)(NCPh) (16)。而錯合物15與三甲基矽氰反應可以得到錯合物Ru(Nacnac)Dipp(NO)(NCTMS) (17)。

A series of Ru(II) complexes supported by amidinate ligand with general formula of Ru[-2-HC(N-2,6-iPr2C6H3)2](6-arene)(X) (X = Cl, arene = p-cymene, 3; benzene, 5; X = OTf, arene = p-cymene, 7) were successfully synthesized. Reduction of Ru[-2-HC(N-2,6-iPr2C6H3)2] (6-arene)(Cl) (3, 5) with KC8 furnished a novel, low coordinate, half sandwich and univalent ruthenium complexes, Ru[-2-HC(N-2,6 -iPr2C6H3)2](6-arene) (arene = p-cymene, 4; benzene, 6). The reaction of Ru[-2-HC(N-2,6-iPr2C6H3)2](6-p-cymene) (4) with organic azides (TMSN3, TMS = trimethylsilane) resulted in the formation of an azido bound complex Ru[-2-HC(N-2,6-iPr2C6H3)2](6-p-cymene) (N3) (9).
After exposure of a solution of Ru[-2-HC(N-2,6-iPr2C6H3)2] (6-p-cymene) (4) to two equivalents of nitric oxide, two products can be isolated: an NO-bridge and NO-binded dinuclear ruthenium complex {(-NO)Ru(NO)[-2-HC(N-2,6-iPr2C6H3)2]}2 (10) with both ruthenium atoms in 18-electron configuration, as well as a hydroxyl-bridged C-H activation complex Ru2(-OH)[-2-HC(N-2,6-iPr2C6H3)][-2-HC (N-2,6-iPr2C6H3)(N-2-(1-CH2)CH3CH-6-iPrC6H3)] (11). Reaction of 4 with excess nitric oxide afforded an organic product HC(N-2,6-iPr2C6H3)[(NO)N-2,6-iPr2C6H3] (12). Moreover, exposure of a solution of 4 to excess carbon monoxide led to the formation of dinuclear complexes {Ru[-2-HC(N-2,6-iPr2C6H3)2C(O)](CO)2}2 (13) and {Ru[-2-HC(N-2,6-iPr2C6H3)2C(O)](CO)3}2 (14).
Furthermore, reaction of [(-NO)Ru(Nacnac)]2 (15) with benzonitrile gave four coordinate and uninucleated complex Ru(Nacnac)Dipp(NO)(NCPh) (16). Upon treatment of 15 with trimethylsilanecarbonitrile (TMSCN), the product Ru(Nacnac)Dipp(NO)(NCTMS) (17) can be obtained.

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