带有三齿双阴离子配体的钌亚烷基化合物：路易斯酸活化与烯烃复分解反应。
Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis.
作者信息
McKinty Adam M, Stephan Douglas W
机构信息
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada.
出版信息
Dalton Trans. 2016 Mar 7;45(9):3844-52. doi: 10.1039/c5dt04481b.
The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis.
制备了一系列钌亚烷基三齿配合物（L）Ru（CHPh）（SCH₂CH₂）₂E（E = O，L = SIMes 1，PCy₃ 2；E = S，L = SIMes 3，PCy₃ 4；E = PPh 7，L = PCy₃）、（L）Ru（CHPh）（SC₆H₄）₂S（L = SIMes 5，PCy₃ 6）、（L）Ru（CHPh）（OCH₂CH₂）₂O（L = SIMes 8，PCy₃ 9），并表明它们与一当量的BCl₃反应生成配合物（L）Ru（CHPh）Cl[E（CH₂CH₂S）₂BCl₂]（E = O，L = SIMes 10，PCy₃ 11；E = S，L = SIMes 12a/b，PCy₃ 13；E = PPh，L = PCy₃ 16）和（L）Ru（CHPh）（SC₆H₄）₂O（L = SIMes 14，PCy₃ 15）。对于1和2，与两当量的BCl₃反应通过氯原子提取得到相应的阳离子。这些阳离子与MeCN配位生成六配位的钌阳离子盐[（L）Ru（CHPh）（NCMe）（O（CH₂CH₂S）₂BCl₂）][BCl₄]（L = SIMes 17，PCy₃ 18）。通过添加两当量的BCl₃从2 - 9衍生得到的生成的五配位阳离子在烯烃复分解催化的标准初步测试中进行了评估。
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