如何有效的利用組會(huì)資源

1、如何合理有效地利用如何合理有效地利用組會(huì)資源組會(huì)資源組會(huì)是研究小組內(nèi)部為加強(qiáng)學(xué)術(shù)交流而組會(huì)是研究小組內(nèi)部為加強(qiáng)學(xué)術(shù)交流而舉行的小型舉行的小型學(xué)術(shù)會(huì)議學(xué)術(shù)會(huì)議 研究工作報(bào)告研究工作報(bào)告 精選文獻(xiàn)報(bào)告精選文獻(xiàn)報(bào)告 其它內(nèi)容其它內(nèi)容 組內(nèi)日常事務(wù)組內(nèi)日常事務(wù) 指導(dǎo)教師對(duì)學(xué)生的要求指導(dǎo)教師對(duì)學(xué)生的要求組會(huì)的形式組會(huì)的形式無(wú)固定模式無(wú)固定模式 小組討論會(huì) 每天一次小組報(bào)告會(huì) 每周一次大組報(bào)告會(huì) 每月一次University of NottinghamMartyn Poliakoff, Steve Howdle and Mike George Richard EisenbergUniversity of

2、Rochester研究工作報(bào)告研究工作報(bào)告精選文獻(xiàn)報(bào)告精選文獻(xiàn)報(bào)告專題報(bào)告專題報(bào)告組會(huì)的形式組會(huì)的形式無(wú)固定模式無(wú)固定模式 組會(huì)的目的組會(huì)的目的提供相互學(xué)習(xí)的機(jī)會(huì)提供相互學(xué)習(xí)的機(jī)會(huì) 演講者應(yīng)認(rèn)真準(zhǔn)備盡量使每位與會(huì)者都能聽得懂演講者應(yīng)認(rèn)真準(zhǔn)備盡量使每位與會(huì)者都能聽得懂 與會(huì)者應(yīng)積極參與討論發(fā)言與會(huì)者應(yīng)積極參與討論發(fā)言給演講者以提高自己的機(jī)會(huì)給演講者以提高自己的機(jī)會(huì) 提高演講與口才的能力提高演講與口才的能力 提高提高PPTPPT的制作能力的制作能力給演講者以歸納整理實(shí)驗(yàn)數(shù)據(jù)的機(jī)會(huì)給演講者以歸納整理實(shí)驗(yàn)數(shù)據(jù)的機(jī)會(huì)給指導(dǎo)教師以把握課題動(dòng)向的機(jī)會(huì)給指導(dǎo)教師以把握課題動(dòng)向的機(jī)會(huì)精選文獻(xiàn)報(bào)告精選文獻(xiàn)報(bào)告研究

3、背景研究背景作者為什么開展這項(xiàng)工作、要解決什么問題作者為什么開展這項(xiàng)工作、要解決什么問題作者采取了什么方法來(lái)解決要解決的問題作者采取了什么方法來(lái)解決要解決的問題作者得到了那些結(jié)論作者得到了那些結(jié)論作者用什么樣的數(shù)據(jù)來(lái)支持所得出的結(jié)論作者用什么樣的數(shù)據(jù)來(lái)支持所得出的結(jié)論你本人對(duì)這項(xiàng)工作的評(píng)價(jià)或意見你本人對(duì)這項(xiàng)工作的評(píng)價(jià)或意見這項(xiàng)工作對(duì)本組的工作有何啟示這項(xiàng)工作對(duì)本組的工作有何啟示研究工作報(bào)告研究工作報(bào)告工作報(bào)告是一段時(shí)間內(nèi)研究工作的工作報(bào)告是一段時(shí)間內(nèi)研究工作的updateupdate或總結(jié)或總結(jié), , 而不是所做而不是所做實(shí)驗(yàn)的羅列，報(bào)告一定要有主題和上下文實(shí)驗(yàn)的羅列，報(bào)告一定要有主題和上下文

4、UpdateUpdate式的報(bào)告式的報(bào)告 上次組會(huì)所講內(nèi)容的簡(jiǎn)單回顧上次組會(huì)所講內(nèi)容的簡(jiǎn)單回顧 本次所做的工作以及做這些工作的目的本次所做的工作以及做這些工作的目的 得到什么樣的結(jié)論得到什么樣的結(jié)論 支持結(jié)論的實(shí)驗(yàn)數(shù)據(jù)支持結(jié)論的實(shí)驗(yàn)數(shù)據(jù) 存在的問題以及解決這些問題的方案存在的問題以及解決這些問題的方案 未來(lái)工作的打算未來(lái)工作的打算研究工作報(bào)告研究工作報(bào)告工作報(bào)告是一段時(shí)間內(nèi)研究工作的工作報(bào)告是一段時(shí)間內(nèi)研究工作的updateupdate或總結(jié)或總結(jié), , 而不是所做而不是所做實(shí)驗(yàn)的羅列，報(bào)告一定要有主題和上下文實(shí)驗(yàn)的羅列，報(bào)告一定要有主題和上下文總結(jié)式的報(bào)告總結(jié)式的報(bào)告 研究背景研究背景 本工

5、作的目的本工作的目的 所采取的方法手段所采取的方法手段 得到的結(jié)論得到的結(jié)論 支持結(jié)論的實(shí)驗(yàn)數(shù)據(jù)支持結(jié)論的實(shí)驗(yàn)數(shù)據(jù) 報(bào)告某具體實(shí)驗(yàn)應(yīng)該采用的模式報(bào)告某具體實(shí)驗(yàn)應(yīng)該采用的模式應(yīng)該采用的模式應(yīng)該采用的模式 我做了我做了XXXX實(shí)驗(yàn)，為什么要做此實(shí)驗(yàn)，應(yīng)用了實(shí)驗(yàn)，為什么要做此實(shí)驗(yàn)，應(yīng)用了XXXX手段手段 我觀察到了我觀察到了XXXX現(xiàn)象，分離到了現(xiàn)象，分離到了XXXX物質(zhì)物質(zhì) 我采用了我采用了XXXX表征手段（表征手段（NMRNMR，IRIR，GC GC 等圖譜）等圖譜） 我得到了我得到了XXXX結(jié)論結(jié)論 請(qǐng)大家討論我得到的結(jié)論請(qǐng)大家討論我得到的結(jié)論我們現(xiàn)有的模式我們現(xiàn)有的模式 我做了我做了XXXX

6、實(shí)驗(yàn)，應(yīng)用了實(shí)驗(yàn)，應(yīng)用了XXXX手段手段 我觀察到了我觀察到了XXXX現(xiàn)象，分離到了現(xiàn)象，分離到了XXXX物質(zhì)物質(zhì) 我采用了我采用了XXXX表征手段（表征手段（NMRNMR，IRIR，GC GC 等圖譜）等圖譜） 請(qǐng)問大家我得到了什么結(jié)論請(qǐng)問大家我得到了什么結(jié)論P(yáng)PTPPT的制作與演講的語(yǔ)言的制作與演講的語(yǔ)言PPTPPT的制作要規(guī)范的制作要規(guī)范統(tǒng)一的格式統(tǒng)一的格式文獻(xiàn)引用的格式要前后一致文獻(xiàn)引用的格式要前后一致盡量用圖表、反應(yīng)式等化學(xué)語(yǔ)言，避免大篇的文字?jǐn)⑹霰M量用圖表、反應(yīng)式等化學(xué)語(yǔ)言，避免大篇的文字?jǐn)⑹鰣D表、反應(yīng)式等化學(xué)語(yǔ)言要做到圖表、反應(yīng)式等化學(xué)語(yǔ)言要做到publishablepublis

7、hable演講時(shí)要用專業(yè)的語(yǔ)言演講時(shí)要用專業(yè)的語(yǔ)言注意培養(yǎng)良好的講臺(tái)風(fēng)范注意培養(yǎng)良好的講臺(tái)風(fēng)范Group Meeting Research TalkUnderstanding the Mechanism of Ni Catalyzed S-C CouplingJie ZhangAug 05, 2010Reaction conditions: 1.0 mmol of PhSH, 1.1 mmol of PhI, 2.0 mmol of base, and 1.0 mmol decane (GC internal standard) in 6 mL of solventA possible mec

8、hanism for PCPNi catalyzed C-S coupling reactionsYields vs time100806040200Yields (%)120100806040200Time (min)How long the catalyst can live actively?GC yields: First run 99%Second run 10% First run 99%Second run 47%PPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0

9、 0.0 -10.0 149.4121 148.8113 148.3036 146.3223 145.7532 140.2617 137.7102 133.4963 133.2138 131.0040 111.3512 47.3304 27.8274 25.1203 10.7871 10.0482 10.0098 6.0158 -5.7510 -5.8932 -6.0632 -6.0934 -6.6989PPh3PPM 148.0 146.0 144.0 142.0 140.0 138.0 136.0 134.0 132.0 1.204 1.617 4.938 4.685 3.229 0.56

10、1 0.702 3.320 149.4121 148.8113 148.3036 146.3223 145.7532 140.2617 137.7102 133.4963 133.2138 131.004031P1H NMR*Reaction of PCPNi-SAr with KOHPh2P(O)-Reaction of PCPNi-SAr with KOHPPM 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 -10.0 149.5039 148.4794 147.94

11、90 147.0338 145.9272 145.8416 140.4366 137.8870 134.3306 131.8554 74.0266 47.4386 25.7824 25.2934 25.1126 11.3128 10.9040 6.7007 -5.6862 -5.7911file: C:GroupZJNMRZJ221215fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumbe

12、r of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.0000PPh3Ph2P(O)-PPM 151.0 149.0 147.0 145.0 143.0 141.0 139.0 137.0 135.0 133.0 131.0 129.0 149.5039 148.4794 147.0338 145.9272 140.4366 137.8870 134.3306 131.8554file: C:GroupZJNMRZJ221215fid expt: trans

13、mitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.000031P1H NMR*18PPM 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0 0.0 -20.0 145.8823 145.78

14、48 140.9848 140.9298 140.8861 140.8539 25.5048 25.4707 25.4355 25.4132 11.5162 11.4496 11.4126 11.3570 11.3143 11.2590 6.8137 6.7667 6.7237 6.6678 6.5602file: C:GroupZJNMRZJ221414fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 H

15、z/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000PPM 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0 0.0 -20.0 148.4425 148.3779 145.8936 140.9600 140.8532 138.3016 27.3768 25.4474 25.4309 11.6620 11.6266 11.5296 6.8045 6.7740file: C:GroupZJNMR

16、ZJ221413fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000Reaction of PCPNi-Cl with KOH2h24h* *PPh3PPh3*21PPM 200.0 160.

17、0 120.0 80.0 40.0 220.2451 220.1985 220.1510 205.4045 187.4503 187.3393 63.1340file: C:GroupZJNMRZJ221614fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768

18、 complex pointsLB: 0.000 GB: 0.0000PPM 200.0 160.0 120.0 80.0 40.0 187.4520 187.4245 187.3429 187.3108 187.2775 63.1254 18.2219file: C:GroupZJNMRZJ221612fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumber of scans: 64fre

19、q. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000PPM 200.0 160.0 120.0 80.0 40.0 220.2292 220.1841 220.1456 205.4188 187.3297 63.1481file: C:GroupZJNMRZJ221616fid expt: transmitter freq.: 161.983672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 pp

20、m = 2.227560 Hz/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000PPM 200.0 160.0 120.0 80.0 40.0 220.1527 220.0002 219.9438 205.4484 187.3253 187.3088 63.1776 62.9151 10.3513 10.3135file: C:GroupZJNMRZJ221617fid expt: transmitter freq.: 161.9

21、83672 MHztime domain size: 32768 pointswidth: 72992.70 Hz = 450.617645 ppm = 2.227560 Hz/ptnumber of scans: 64freq. of 0 ppm: 161.975573 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.00000.5 h7 h24 h48 hFuture WorkSynthesis of possible intermediates involved in the catalytic processMore det

22、ails for the catalyst decompose process by GC-MS Photocatalytic Hydrogen Generation from Water Using Platinum Bipyridyl Acetylide ComplexesJie Zhang Eisenberg Group MeetingJuly 25, 2006Multiple component systems for photochemical water splitting using visible light:The chromophore Ru(bpy)32+ Electro

23、n transfer mediatorMethyl viologen (MV2+) Metal colloidal catalystPtSacrificial electron donor TEOAPtNNOOOOOOOONHR =(1)(2)(3)RRHMeJ. Am. Chem. Soc., 2006, 128, 7726SynthesisNNPtCl2(DMSO)2+PtClClOOOONNOOOOMeOH/CH2Cl2RRPtNNOOOORC6H4CCHCuI, Et3N, CH2Cl2OOOONHOOOONHPtNNOOOOaabbccddeeffgggfhhiiijjjkkH2OD

24、MSOPtNNOOOOH2ODMSOaabbccddeefffggghhH2OCDCl3PtNNOOOOaabbccddeefffggghhReactivityOOOONHOOOONHPtNNOOOOOOOONHOOOONHPtNNOONaOONaTHF/H2O/NaOHOOOONHOOOONHPtNNOOHOOHNaOHHClOOOONHOOOONHPtNNOOHOOHaabbccdddeeeffggghhhiiH2ODMSOOOOONHOOOONHPtNNOOHOOHOOOONHOOOONHPtNNOOOOAbsorption and emission spectra in THF/H2O

25、 (1/1)Absorption and emission spectra in MeCNPtNNOOOO1.7 10-5 MAbsorption and emission spectra in MeCN1.9 10-5 MPtNNOOOOAbsorption and emission spectra in MeCNPtNNOOOOPtNNOOOOEmission spectra of Ptbpy(COOEt)2(CCPh)2 in MeCN/H2OAbsorption spectra of Ptbpy(COOEt)2(CCPh)2 different solventReductive que

26、nching of Ptbpy(COOEt)2(CCPh)2 by TEOA in MeCNReductive quenching of Ptbpy(COOEt)2(CCPh)2 by TEOA in MeCNStern-Volmer equation: I0em/Iem = 1 + 0kqQOxidative quenching of Ptbpy(COOEt)2(CCPh)2 by 3-Nitrobenzaldehyde in MeCNOxidative quenching of Ptbpy(COOEt)2(CCPh)2 by 3-Nitrobenzaldehyde in MeCNStern

27、-Volmer equation: I0em/Iem = 1 + 0kqQPtNNOOOOPtNNOOOOEstimate kq value in Stern-Volmer equationStern-Volmer equation: I0em/Iem = 1 + 0kqQ0 = ?0 = 20 nsInorg. Chem., 2001, 40, 4053TEOAkq = 7.12 109 M-1 s-13-Nitrobenzaldehyde kq = 3.15 109 M-1 s-1Water reduction using Ptbpy(COOEt)2CCC6H4NHC(O)C6H2(OMe

28、)32Chromophore:2.3 10-5 MMV2+: 3.1 10-4 MTEOA: 5.6 mMPt colloid: 6.0 10-5 MSolvent: THF/H2O (2/3)pH 7 with buffer solutionRadiation: 410 nm for 7 hours, no blue color, no H2OOOONHOOOONHPtNNOOHOOHWater reduction using Ptbpy(COOEt)2(CCPh)2Chromophore:PtNNOOOO1.8 10-5 MMV2+: 3.3 10-4 MTEOA: 10.7 mMPt c

29、olloid: 3.0 10-5 MSolvent: MeCN/H2O (4/1)pH8 without adding buffer solutionRadiation: 410 nm, blue color developed, H2 generatedTurnover number: 1 mol H2/Pt; 1.7 mol H2/chromophoreWater reduction using Ptbpy(COOEt)2(CCPh)2Water reduction using Ptbpy(COOEt)2(CCC6H4Me)2Chromophore:1.5 10-5 MMV2+: 3.3

30、10-4 MTEOA: 12.3 mMPt colloid: 3.0 10-5 MSolvent: MeCN/H2O (4/1)pH8 without adding buffer solutionRadiation: 410 nm for 24 hours, blue color developed, no H2PtNNOOOOFuture workWith Ptbpy(COOEt)2(CCPh)2Optimize reaction condition so as to generate H2 more efficiently:MV2+ concentration, pH, With Ptbp

31、y(COOEt)2(CCC6H4Me)2 Ptbpy(COOEt)2CCC6H4NHC(O)C6H2(OMe)32find the proper condition to generate H2 Synthesis of new chromophor with different substitution in bpy ligand and test their activity in H2 generation. Ancillary Ligand and Ketone Substituent Effects on the Rate of Ketone Insertion into Zr-C

32、Bonds of Zirconocene-1-aza-1,3-diene ComplexesJie ZhangGuan Group Meeting02-19-2009ElectrophilicNucleophilicumpolungR1R2NR3R1R2NR3ZrLnR1R2NR3R1R2NR3LnZrReactivity Umpolung Induced by ZirconiumEnders, Angew. Chem. Int. Ed., 1998, 37, 1673 The Ansa-Effect in Metallocene ChemistryIncorporation of an an

33、sa bridge may increase the reactivity of metallocences by creating a more Lewis acidic metal center providing a more spacious equatorial siteM M L LnA AM M L Ln The rotation of Zr-Ph bond in Me2Si(C5Me4)2ZrPh2 is about 400 times faster than that of Cp*2ZrPh2 Dalton Trans., 2000, 4490. H2 is much eas

34、ier to be eliminated from Me2Si(C5Me4)2Mo(2-H2)(H)+ compared with Cp*2MoH3+ JACS, 2004, 126, 13054. Me2Si(C5H4)2ZrCl2/MAO is a better catalyst for ethylene polymerization than Cp2ZrCl2/MAO (MAO = methylalumoxane) Macromol. Rapid Commun., 1995, 16, 357.New Challenges Can other electrophiles insert in

35、to the Zr-C bond in the zirconocene azadiene complex? How ansa-bridging and other ancillary ligands influence the reactivity of the zirconocene azadiene complex? What is the mechanism of ketone insertion into Zr-C bond in the zirconocene azadiene complex? Synthesis of Zirconocene-1-aza-1,3-diene Com

36、plex2a (R = H, 69%)2b (R = OCH3, 77%) 2c (R = NO2, not formed)2d (R = CF3, not formed) 3a (R = H, 73%)3b (R = OCH3, 85%)3c (R = NO2, not formed)3d (R = CF3, formed but decomposed)X-Ray Structure of Zirconocene-1-aza-1,3-diene ComplexZrNPhSiZrNPhZrNPhOMe2a3a3bSelected bond lengths() and Dihedral Angl

37、e () Zr-N1Zr-C1Zr-C2Zr-C3C1-C2Cp1 & Cp2N1-C3-Zr&N1-C1-C2-C32a2.133(5)2.570(7)2.576(7)2.320(6)1.3661.3(3)55.4(4)3a2.129(2)2.5886(29)2.6997(29)2.321(3)1.3855.41(13)54.64(15)3b2.129(3)2.568(3)2.583(3)2.329(3)1.3856.5(13)57.15(16)1H NMR Spectra of Zirconocene-1-aza-1,3-diene ComplexSpinWorks 2.5: PPM 7.

38、6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 1.000 3.029 4.248 1.017 4.291 1.093 4.760 2.028 2.083 7.2577 7.2379 7.2192 7.0948 7.0766 6.9129 6.8946 6.8763 6.8439 6.8376 6.8214 6.8058 6.7898 6.7831 6.0300 6.0262 6.0137 6.0099 5.9685 5.9514 5.5776 5.5610 5.5547 5.5381 5.44

39、63 5.4293 5.2962 5.2936 3.7838 3.7675 1.4428 1.4397 1.4199 1.4168file: C:UsersorganometallicsDesktopZJNMRZJ0482fid expt: transmitter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 ppm = 0.126314 Hz/ptnumber of scans: 16freq. of 0 ppm: 400.130024 MHzprocessed size: 3

40、2768 complex pointsLB: 0.300 GB: 0.0000ZrNPhOMe3b1H NMR Spectra of Zirconocene-1-aza-1,3-diene ComplexPPM 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 -0.0 2.999 2.921 1.074 0.962 0.966 2.887 0.984 1.037 1.011 1.005 1.022 4.239 6.200 7.3243 7.3052 7.2953 7.2904 7.2849

41、7.2765 7.2750 7.2563 7.1871 7.1601 7.0394 7.0341 7.0317 7.0231 7.0178 7.0132 7.0110 6.9636 6.2761 6.2717 6.2686 6.1633 6.1614 6.1581 6.1563 5.9055 5.9015 5.8888 5.8848 5.6622 5.6598 5.6548 5.6524 5.5361 5.5340 5.5309 5.5287 5.4534 5.4497 5.4463 5.4414 5.4334 5.4308 5.4264 5.4210 5.4195 5.4106 5.0688

42、 5.0658 5.0613 5.0584 4.6157 4.6132 4.6107 4.6083 1.6071 1.6036 1.5841 1.5806 0.4366 0.4284 0.0054 -0.0026file: C:UsersorganometallicsDesktopZJNMRZJ-Me2SiCp2ZrNPhCHCHCHPh4fid expt: transmitter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 ppm = 0.126314 Hz/ptnumber

43、 of scans: 16freq. of 0 ppm: 400.130044 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000ZrNPhSi2aSelective Homonuclear Decoupling 1H NMR SpectraZrNPhSi2aPossible Solution Structure of Zirconocene-1-aza-1,3-diene Complex The ring flipping is fast at the NMR time scale and the average A/A a

44、nd B/B resonances has been observed The equilibrium mixture of A/A and B/B is established but one pair is highly populated There is a high kinetic barrier for A/AB/B interconversion and one of the two pairs is kinetically formed during the synthesisVT NMR of 2a (60C-70C) showed no difference DFT Cal

45、culationThe equilibrium mixture of A/A and B/B is established but one pair is highly populatedReactivity of Zirconocene-1-aza-1,3-diene ComplexZrNPhRSiPh2COToluene, 80oCZrONRSiPhPhPhZrNPhRPh2COZrONRPhPhPhToluene, 80oC4a (R = H, 87%)4b (R = OCH3, 88%) 5a (R = H, 91%)5b (R = OCH3, 90%) 5a Zr-N1: 2.17

46、; Zr-O1: 1.96 Cp1&Cp2: 52.9Reactivity of Zirconocene-1-aza-1,3-diene ComplexZrNPhPhSiZrNNPhSiPhRNZrONPhSiOEtPhRR = Me, PhOOZrONPhSiOtBuPhOOZrNPhSiPhorOOtBuBrZrNPhSiPhBrOZrONPhSiPhZrNPhSiPhOorCO2ZrONPhSiPhOOOOZrONPhSiPhOOZrONPhSiPhCOClOZrONPhSiPhClOZrNPhSiPhOPhZrNPhSiPhPhPhPhZrNPhSiPhPhPhPPM 7.6 7.2

47、6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 1.000 1.714 1.714 0.380 0.395 0.394 7.8339 7.8294 7.8275 7.8262 7.8227 7.8138 7.8088 7.8051 7.2704 7.2581 7.2546 7.2513 7.2418 7.2362 7.2311 7.2211 7.2178 7.2143 7.1690 7.1659 7.1646 7.1610 7.1486 7.1453 7.1416 7.1348 7.1313 7.1274

48、7.1250 5.7473 5.1848 2.2221file: C:UsersorganometallicsDesktopZJNMRZJ063-11fid expt: transmitter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 ppm = 0.126314 Hz/ptnumber of scans: 16freq. of 0 ppm: 400.130000 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.0

49、000PPM 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 1.000 0.110 7.8343 7.8296 7.8265 7.8232 7.8142 7.8091 7.8055 7.2703 7.2667 7.2572 7.2538 7.2506 7.2410 7.2355 7.2302 7.2203 7.2170 7.2135 7.1683 7.1652 7.1637 7.1603 7.1478 7.1446 7.1408 7.1306 7.1265 7.1243 6.3143 5.

50、9117 2.2221file: C:UsersorganometallicsDesktopZJNMRZJ063-12fid expt: transmitter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 ppm = 0.126314 Hz/ptnumber of scans: 16freq. of 0 ppm: 400.130000 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.0000ZrNOZrNO+Tolu

51、ene-d8110Kinetic Study of Ketone Insertion into Zr-C Bond of Zirconocene-1-aza-1,3-diene ComplexPPM 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 -0.0 1.000 1.044 1.027 0.308 0.335 1.005 0.322 0.346 0.321 0.306 0.304 7.8498 7.8332 7.8288 7.8258 7.8133 7.8083 7.8047 7.43

52、11 7.4120 7.4030 7.3916 7.3842 7.3679 7.3642 7.2918 7.2701 7.2580 7.2546 7.2513 7.2417 7.2363 7.2311 7.2210 7.2178 7.2143 7.1886 7.1644 7.1610 7.1484 7.1453 7.1417 7.1312 7.1273 7.1250 7.1144 7.0901 7.0874 7.0690 7.0506 6.3830 6.3787 6.3756 6.3711 6.2888 6.2833 6.2820 6.0226 6.0186 6.0059 6.0019 5.7

53、849 5.7827 5.7778 5.6606 5.6585 5.6533 5.5732 5.5682 5.5630 5.5563 5.5501 5.5434 5.5384 5.5333 5.5271 5.1905 5.1831 5.1785 5.1756 5.1710 4.7255 4.7231 4.7204 4.7182 4.7132 2.2220 1.7178 1.7144 1.6947 1.6913 0.5626 0.5541 0.1292 0.1209file: C:UsersorganometallicsDesktopZJNMRZJ063-21fid expt: transmit

54、ter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 ppm = 0.126314 Hz/ptnumber of scans: 16freq. of 0 ppm: 400.130000 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.0000PPM 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 -0.0 1.000

55、 7.8474 7.8339 7.8294 7.8264 7.8229 7.8139 7.8089 7.8052 7.7748 7.7714 7.7534 7.4445 7.4337 7.4252 7.4202 7.3816 7.3631 7.3607 7.3423 7.2907 7.2810 7.2701 7.2573 7.2540 7.2507 7.2411 7.2357 7.2304 7.2205 7.2171 7.2137 7.2059 7.1862 7.1683 7.1639 7.1604 7.1480 7.1448 7.1410 7.1307 7.1268 7.1244 7.113

56、3 7.1095 7.0912 7.0607 6.9740 6.9558 6.8970 6.8945 6.8758 6.8737 6.8240 6.8195 6.8116 6.8037 6.7986 6.2099 6.2007 6.1805 6.1744 2.2221 0.6296 0.4527file: C:UsersorganometallicsDesktopZJNMRZJ063-22fid expt: transmitter freq.: 400.132471 MHztime domain size: 65536 pointswidth: 8278.15 Hz = 20.688513 p

57、pm = 0.126314 Hz/ptnumber of scans: 16freq. of 0 ppm: 400.130000 MHzprocessed size: 32768 complex pointsLB: 0.300 GB: 0.0000ZrNSiOZrNOSi+Toluene-d8110Kinetic Study of Ketone Insertion into Zr-C Bond of Zirconocene-1-aza-1,3-diene Complex1.00.80.60.40.20.0Normalized Relative Intensity of Si-CH314x103

58、121086420Time (s)Disappearance of zirconacycle 2a as a function of time in toluene-d8 at 60CZrNSiOZrNOSi+Toluene-d81102a = 1.4010-2M2a = 3.0010-2M2a = 3.8010-2M2a = 4.6010-2MUnder pseudo-first-order conditionsthe disappearance of 2a follows exponential decay. 6.0 x10-45.04.03.02.01.00.0kobs (s-1)0.5

59、0.40.30.20.1Concentration of Ph2CO (M)Plots of kobs as a funcation of PhCOPh concentration in toluene-d8 at 60Ck(M-1s-1)2a1.3 10-33a4.6 10-42b3.0 10-43b1.7 10-4The ansa-bridged Cp systems are more reactive than the bisCp systems: insertion rates for 2a and 2b are about 2.8 and 1.8 times faster than

60、3a and 3b, respectively.An electron-rich aryl group on N disfavors ketone insertion: insertion rates for 2a and 3a are about 4.3 and 2.7 times faster than 2b and 3b, respectively. ZrNPhSiZrNPhOMeSiZrNPhZrNPhOMe2a3b3a2b8x10-46420kobs (s-1)0.50.40.30.20.1Concentration of Ph2CO (M)-13.0-12.5-12.0-11.5-