synthesis of univalent ruthenium complexes and reactivity study

• Main Authors: Yang, Kuang-Hao, 楊廣浩
• Other Authors: 蔡易州
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/73641394438110905022

碩士 === 國立清華大學 === 化學系 === 100 === 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.