[N、C、N]型双亚胺钯、铂钳形化合物的合成及其在碳-碳偶合中的应用.pdf

《[N、C、N]型双亚胺钯、铂钳形化合物的合成及其在碳-碳偶合中的应用.pdf》由会员上传分享，免费在线阅读，更多相关内容在工程资料-天天文库。

1、໽⋹໻ᄺ⸩຿ᄺԡ䆎᭛[NǃǃǃCǃǃǃN]ൟঠѮ㛎䪃ൟঠѮ㛎䪃ǃൟঠѮ㛎䪃ǃǃǃ䪖䪇ᔶ࣪ড়⠽䪖䪇ᔶ࣪ড়⠽ⱘড়៤ঞ݊೼⺇-⺇يড়Ёⱘᑨ⫼C-Hbondactivationof1,3-bisimines:synthesis,characterizationof3,5-dimethyl-2,6-bis(N-arylimnio)phenylpalladium(II)andplatinum(II)chlorideandtheircatalysisincarbon-carboncrosscoup

2、lingᄺ⾥ϧϮ˖᳝ᴎ࣪ᄺⷨお⫳˖䰜ὩᣛᇐᬭᏜ˖⥟⋾᯳ࡃᬭᥜ໽⋹໻ᄺ⧚ᄺ䰶2012ᑈ5᳜⣀߯ᗻໄᯢᴀҎໄᯢ᠔ਜѸⱘᄺԡ䆎᭛ᰃᴀҎ೼ᇐᏜᣛᇐϟ䖯㸠ⱘⷨおᎹ԰੠পᕫⱘⷨお៤ᵰˈ䰸њ᭛Ё⡍߿ࡴҹᷛ⊼੠㟈䇶П໘໪ˈ䆎᭛Ёϡࣙ৿݊ҪҎᏆ㒣থ㸼៪᪄ݭ䖛ⱘⷨお៤ᵰˈгϡࣙ৿Ў㦋ᕫඟࠣӖ༰៪݊Ҫᬭ㚆ᴎᵘⱘᄺԡ៪䆕к㗠Փ⫼䖛ⱘᴤ᭭DŽϢ៥ϔৠᎹ԰ⱘৠᖫᇍᴀⷨお᠔خⱘӏԩ䋵⤂ഛᏆ೼䆎᭛Ё԰њᯢ⹂ⱘ䇈ᯢᑊ㸼⼎њ䇶ᛣDŽᄺԡ䆎᭛԰㗙ㅒৡ˖ㅒᄫ᮹ᳳ˖ᑈ᳜᮹ᄺԡ䆎᭛⠜ᴗՓ⫼ᥜᴗкᴀ

3、ᄺԡ䆎᭛԰㗙ᅠܼњ㾷ඟࠣӖ༰᳝݇⬭ǃՓ⫼ᄺԡ䆎᭛ⱘ㾘ᅮDŽ⡍ᥜᴗඟࠣӖ༰ৃҹᇚᄺԡ䆎᭛ⱘܼ䚼៪䚼ߚݙᆍ㓪᭄ܹ᳝݇᥂ᑧ䖯㸠Ẕ㋶ˈᑊ䞛⫼ᕅॄǃ㓽ॄ៪ᠿᦣㄝ໡ࠊ᠟↉ᄬǃ∛㓪ҹկᶹ䯙੠׳䯙DŽৠᛣᄺ᷵৥೑ᆊ᳝݇䚼䮼៪ᴎᵘ䗕Ѹ䆎᭛ⱘ໡ॄӊ੠⺕ⲬDŽ˄ᆚⱘᄺԡ䆎᭛೼㾷ᆚৢ䗖⫼ᴀᥜᴗ䇈ᯢ˅ᄺԡ䆎᭛԰㗙ㅒৡ˖ᇐᏜㅒৡ˖ㅒᄫ᮹ᳳ˖ᑈ᳜᮹ㅒᄫ᮹ᳳ˖ᑈ᳜᮹Ё᭛Ё᭛ᨬ㽕Ё᭛ᨬ㽕䪇ൟ䞥ሲ࣪ড়⠽˄Pincercomplexes˅೼䇌໮乚ඳ᳝ⴔᑓ⊯ⱘᑨ⫼DŽⳌ↨[PǃCǃP]ൟҹঞ[SǃCǃS]ൟ࣪ড়⠽ˈⳂࠡ䆹乚ඳⱘⷨおЏ㽕䲚Ё೼[N

4、ǃCǃN]ൟ࣪ড়⠽DŽᴀ᭛ҹ䯈Ѡ⬆㣃Ўॳ᭭ˈ㒣䖛ϔ㋏߫ডᑨ᳔㒜ᕫࠄᮄൟ[NǃCǃN]ൟ䜡ԧ>4,6Ѡ⬆෎1,3ঠ4’পҷ㣃෎ঠѮ㛎@㣃DŽ䆹࣪ড়⠽Ϣ䝟䝌䪃䗮䖛Ⳉ᥹C-H⌏࣪ᕫࠄ[NǃCǃN]ൟⱘ⦃䪃࣪⠽ˈৢ㗙Ϣ∃࣪䫖ডᑨᕫࠄⳌᑨⱘ∃ҷ⦃䪃࣪ড়⠽DŽᑊ೼ℸ෎⸔Ϟᠽሩ䆹ⷨおᮍ⊩˄Ⳉ᥹C-H⌏࣪˅ⱘᑨ⫼㣗ೈˈᓔሩњ5⸱෎5নϕ෎পҷঠѮ㛎ⱘ䪃࣪ˈᑊᬊࠄњЁㄝᬊ⥛ˈৠᯊг䆕ᅲ䆹ԧ㋏г䗖⫼Ѣ⫳៤113⦃䪖࣪ড়⠽DŽϞ䗄৘ℹѻ⠽ⱘ㒧ᵘഛ㒣䖛IRǃH-NMRǃC-NMR䆕ᅲDŽⷨお䖭⾡ᮄൟ[Nǃ

5、CǃN]䪇ൟ⦃䪃࣪ড়⠽ڀ࣪ⱘ㢇෎सҷ⠽Ϣ㣃⹐䝌ⱘSuzukiي㘨ডᑨˈҹᇍ⬆෎⒈㣃Ϣ㣃⹐䝌ⱘডᑨ԰Ў՟ᄤˈ᥶㋶њ᳔ՇӬ࣪ᴵӊˈᑊϨ೼ℸ෎⸔Ϟ᥶おњ㋏߫㢇स˄X=BrǃCl˅Ϣ㣃⹐䝌ⱘSuzukiي㘨ডᑨDŽৠᯊ᥶おњ䆹㋏߫⦃䪃࣪ড়⠽೼ڀ࣪㢇स˄X=BrǃCl˅Ϣϭ⛃䝌⬆䝃ⱘHeckي㘨ডᑨDŽ㒧ᵰ㸼ᯢ䆹㋏߫䪃࣪⠽ᰃSuzukiي㘨ডᑨⱘӬ㡃ڀ࣪ࠖˈৠᯊᇍHeckي㘨ডᑨг㛑পᕫ䕗དⱘᬊ⥛DŽ݇䬂䆡݇䬂䆡˖݇䬂䆡˖˖˖[NǃCǃN]䜡ԧ˗⦃䞥ሲ࣪˗[NǃCǃN]䪇ൟ࣪ড়⠽˗SuzukiHeckي㘨

6、ডᑨABSTRACTPincercomplexarewidelyusedinmanyfields.Comparedtothe[P┚C┚P]and[S┚C┚S]analogues,[N┚C┚N]pincershaveattractedmuchattentioninrecentyears.Inthispaper,wehavesynthesizedtheligands,4,6-dimethyl-1,3-bis(N-arylimino)benzenesfromthestaringmaterialm-x

7、yleneafterseveraltransformations.Treatmentoftheseligandswithpalladiumacetate(II)inanhydrousaceticacidandfollowedbylithiumchlorideresultedinthecorresponding[N┚C┚N]palladium(II)pincer,i.e.,3,5-dimethyl-2,6-bis(N-arylimino)isophthalaldimin-2-ylpalladium(

8、II)chlorideinmoderateyields.Inaddition,suchreactionconditionwasalsosuitablefor5-nitroand5-tert-butylbisiminesligands.Alloftheseligandsandtheircorrespondingpincerswerefullycharacterizedbyelementalanalysis,IRandNMR.Thecatalyticefficiencyof3,5-di