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Synthesis, structure, and reactivity of Ru~(II) complexes with trimethylsilylethinylamidinate ligands

机译:Ru〜(II)与三甲基甲硅烷基亚氨基ami酸酯配体的合成,结构和反应性

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摘要

The mononuclear amidinate complexes [(η~6-cymene)-RuCl(1a)] (2) and [(η~6-C_6H_6)RuCl(1b)] (3), with the trimethylsilyl-ethinylamidinate ligands [Me_3SiC≡CC(N-c-C_6H_(11))_2] - (1a -) and[Me_3SiC≡CC(N-i-C_3H)_7)_2] - (1b -) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(η~5- C_5H_5)Ru(PPh_3)(1b)] (4a) [(η~5- C_5Me_5)Ru(PPh_3)(1b)] (4b), and [(η~6-C_6H_6)Ru(PPh_3)(1b)](BF_4) (5-BF_4) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl-silyl group using [Bu_4N]F resulted in the isolation of [(η~6-C_6H_6)Ru(PPh_3){(N-i-C_3H_7)_2CC≡CH}](BF_4) (6-BF_4) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a/b to 6-BF_4 were characterized by multinuclear NMR (~1H, ~(13)C,~(31)P) and IR spectroscopy and elemental analyses, including X-ray diffraction analysis of 1b, 2, and 3.
机译:单核a酰胺配合物[(η〜6-cymene)-RuCl(1a)](2)和[(η〜6-C_6H_6)RuCl(1b)](3),以及三甲基甲硅烷基乙炔基ami酰胺配体[Me_3SiC≡CC( Nc-C_6H_(11))_ 2]-(1a-)和[Me_3SiC≡CC(Ni-C_3H)_7)_2]-(1b-)通过盐复分解法高产率合成。此外,相关的膦配合物[(η〜5- C_5H_5)Ru(PPh_3)(1b)](4a)[(η〜5- C_5Me_5)Ru(PPh_3)(1b)](4b)和[[η通过配体交换反应制备了〜6-C_6H_6)Ru(PPh_3)(1b)](BF_4)(5-BF_4)。使用[Bu_4N] F去除三甲基甲硅烷基的研究导致[[η〜6-C_6H_6)Ru(PPh_3){(Ni-C_3H_7)_2CC≡CH}](BF_4)(6-BF_4 )带有末端炔基氢原子,而2和3则显示出复杂的反应混合物。化合物1a / b至6-BF_4通过多核NMR(〜1H,〜(13)C,〜(31)P)和IR光谱及元素分析(包括1b,2和3的X射线衍射分析)进行表征。

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