第一部份我們合成了一系列含氮膦之鋯、鉿錯合物。首先利用依序在[iPr-PNP]H
( [iPr-PNP]- = bis(o-diisopropylphosphinophenyl)amide ) 的甲苯溶液中加入正丁基鋰與
ZrCl4(THF)2 或HfCl4(THF)2，而可以得到[iPr-PNP]ZrCl3 和 [iPr-PNP]HfCl3。利用UV-Vis
吸收光譜、放光光譜、激發光譜、循環伏安實驗以及密度泛函理論計算來探討此二化合
物具有之磷光光物理性質。另外，此二化合物之同烷三烷基取代衍生物 [iPr-PNP]MR3, R
= Me, CH2SiMe3) 或二烷基取代衍生物 [iPr-PNP]M(E)(R)2, R = CH2SiMe3, E = Cl, Me)
在我們利用立體效應之控制之下，被成功地合成與鑑定。從X-ray 繞射結構與變溫核磁
共振實驗中，化合物的強流變性質引起我們對其反應機構，以及此流變性質對我們反應
性的影響來研究。另外，我們利用加熱[iPr-PNP]Zr(Cl)(CH2SiMe3)2 的實驗，成功的合成
了新的亞烷基化合物[iPr-PNP]M(Cl)(=CHSiMe3)。接著利用變溫分析的方法，我們得到
其活化能為ΔH‡ = 18.5 kcal/mol 和ΔS‡ = -19.8 cal/mol·K。並且也探討在加熱
[iPr-PNP]M(Me)(CH2SiMe3)2 後所觀察到具有多個亞烷基化合物的結果。
在第二部分，我們利用電子泛函密度理論(DFT)的計算來探討[MeNPiPr]Ni(R)(L)
([MeNPiPr]- = o-diisopropylphosphino-2,6-dimethylanilite, R = Me, CH2SiMe3; L =
2,4-Lutidine, Py, PMe3)的碳氫鍵活化反應。始於解離機構，有四個反應階段、與三個主
要的反應機構。包含錯合物的異構化、直接的分子間活化苯、以及分子內sp3 碳氫鍵的
活化，並且解釋氫-氘交換的實驗是如何發生。利用這些計算出來的反應中間體與過渡
態來了解我們的反應，並能支持我們的實驗證據。

A series of tetravalent zirconium and hafnium complexes were developed in their
abundant chemistry and photophysical properties, where those complexes were supported by
diarylamido-phosphino [iPr-PNP]- (bis(o-diisopropylphosphinophenyl)amide) ligand.
[iPr-PNP]MCl3 (M = Zr, Hf) were prepared by sequentially reacting [iPr-PNP]H with
n-butyllithium and following MCl4(THF)2 in toluene solution under ambient temperature.
UV-Vis absorption, emission, excitation spectrum, cyclic voltammetry experiments, and
density functionalization theory (DFT) calculations are applied to approach their unique
photophysical phosphorescence properties. Alkyls which are lack of β-hydrogen have been
used to achieve in synthesis of degenerate ([iPr-PNP]MR3, R = Me, CH2SiMe3) or
non-degenerate ([iPr-PNP]M(E)(R)2, R = CH2SiMe3, E = Cl, Me) derivatives since we could
control the desired product from steric effect. Strong fluxional exchange was found in those
complexes. By variable temperature NMR monitoring and X-ray diffraction, their
fluxionality seems interesting not only in mechanism, but it does affect our reaction. By
heating [iPr-PNP]Zr(Cl)(CH2SiMe3)2 in solution, we can afford new alkylidene complexes
[iPr-PNP]M(Cl)(=CHSiMe3) via self α-abstraction. Through variable temperature analysis,
the activation energy of α-abstraction have ΔH‡ = 18.5 kcal/mol and ΔS‡ = -19.8 cal/mol·K.
Here we also can identified multiple alkylidene derivatives of [iPr-PNP]Zr(Me)(=CHSiMe3)2.
The computational studies of [MeNPiPr]Ni(R)(L) ([MeNPiPr]- = o-diisopropylphosphinoII
phenyl-2,6-dimethylanilite, R = Me, CH2SiMe3; L = 2,4-Lutidine, Py, PMe3) in C-H
activation has been fully established. Start on dissociation mechanism, we considered three
major pathways to explain the activation mechanisms including isomerisation, direct
intermolecular benzene activation, and intramolecular sp3 C-H acitvaition. Here we also
account H-D exchange as experimental observation. Important intermediates and transition
states are found to locate the energy maps to assist our experiments.

Abstract I
Contents IV
Figures Directory X
Table Directory XII
I Introduction 1
I-1 Amido-phosphino Chelating Ligands 3
I-2 C-H activation by Group 4 Complexes Bearing Chelating Ligands 4
I-3 Arene activation by Amido-phosphino Nickel(II) Complexes 5
II Results and Discussion 7
II-1 Amido-diphosphino Zirconium and Hafnium Complexes 7
II-1-1 Synthesis of [iPr-PNP]MCl3 (M=Zr, Hf) 7
II-1-2 Electronic configuration studies of complexes 1 and 2 10
II-1-3 Synthesis of homoalkyl [iPr-PNP]MCl3 derivatives (M = Zr, Hf) 15
II-1-4 Synthesis of mixed-alkyl [iPr-PNP]MCl3 derivatives (M = Zr, Hf) 20
II-1-5 Fluxionality and mechanism 24
II-1-6 Synthesis of zirconium alkylidene complexes 27
II-2 Computational Study of Diarylamido-phosphino Nickel Complexes 34
II-2-1 Net reaction of [MeNPiPr]Ni(Lu)(R) in C-H activation 38
II-2-2 Stage 1 and 4: Association and dissociation of Lewis base 39
II-2-3 Stage 2: Intramolecular C-H activation 40
II-2-4 Stage 3: Intermolecular C-H activation 42
II-2-5 Deuteration cycle 46
III Conclusions 47
IV Experiment Section 49
IV-1 General Procedures 49
IV-2 Instruments 49
IV-3 Computational Methodology 50
IV-4 Synthesis of [iPr-PNP]ZrCl3 (1) (YCH-1-184) 51
IV-5 Synthesis of [iPr-PNP]HfCl3 (2) ( YCH-1-185) 52
IV-6 Synthesis of [iPr-PNP]ZrMe3 (3) (YCH-1-331) 53
IV-7 Synthesis of [iPr-PNP]HfMe3 (4) (YCH-1-310) 53
IV-8 Synthesis of [iPr-PNP]Zr(CH2SiMe3)3 (7) 54
IV-9 Synthesis of [iPr-PNP]Zr(Cl)(CH2SiMe3)2 (5) (YCH-2-5) 55
IV-10 Synthesis of [iPr-PNP]Hf(Cl)(CH2SiMe3)2(6) (YCH-1-334) 56
IV-11 Synthesis of [iPr-PNP]Zr(CH3)(CH2SiMe3)2 (8) (YCH-2-75) 57
IV-12 Synthesis of [iPr-PNP]Hf(CH3)(CH2SiMe3)2 (9) (YCH-2-66) 58
IV-13 Synthesis of [iPr-PNP]Zr(Cl)(=CHSiMe3)2 (10) (YCH-2-55) 59
V References 61
VI Appendix 68
VI-1 Equilibrium of [Ph-PNN]PtCl in the Presence of SMe2 68
VI-2 Kumada Coupling by [Ph-PNN]NiCl 69
VI-3 Kinetic Study of Benzene C-H Activation by [iPr-PNP]NiH 71
VI-4 Dynamic Variable Temperature NMR Data 74
VI-4-1 Activation parameter calculation detail 74
VI-4-2 [iPr-PNP]ZrMe3 (3) 193 K- 363 K in toluene-d8 75
VI-4-3 [iPr-PNP]HfMe3 (4) 193 K - 363 K in toluene-d8 79
VI-4-4 [iPr-PNP]Zr(Cl)(CH2SiMe3)2 (5) 193 K - 363 K in toluene-d8 84
VI-4-5 [iPr-PNP]Hf(Cl)(CH2SiMe3)2 (6) 213 K - 363 K in toluene-d8 91
VI-4-6 [iPr-PNP]Zr(Me)(CH2SiMe3)2 (8) 193 K - 363 K in toluene-d8 93
VI-4-7 [iPr-PNP]Hf(Me)(CH2SiMe3)2 (9) 193 K - 363 K in toluene-d8 99
VI-5 UV-Vis Absorption, Emission, and Excitation Spectrum 104
VI-6 Crystallographic Data 106
VI-6-1 Crystallographic Data of [iPr-PNP]Zr(Cl)(CH2SiMe3)2 108
VI-6-2 Crystallographic Data of [iPr-PNP]Hf(Cl)(CH2SiMe3)2 125
VI-6-3 Crystallographic Data of [iPr-PNP]Zr(CH2SiMe3)3 142
VI-6-4 Crystallographic Data of [iPr-PNP]Zr(Me)(CH2SiMe3)2 158
VI-6-5 Crystallographic Data of [iPr-PNP]Hf(Me)(CH2SiMe3)2 175
VI-6-6 Crystallographic Data of [iPr-PNP]Hf(Me)(CH2SiMe3)2 192
VI-7 Computational Details 209
VI-7-1 Geometry optimized energy in different b3lyp/6-31g**, b3lyp/6-311g** and m06/6-311g** level 209
VI-7-2 [iPr-PNP]ZrCl3 (1) 216
VI-7-3 [iPr-PNP]HfCl3 230
VI-7-4 [MeNPiPr]Ni(Lutidine)(CH2SiMe3) (a) 244
VI-7-5 [MeNPiPr]Ni(CH2SiMe3) (a1) 247
VI-7-6 [MeNPiPr]Ni(CH2SiMe3) (a1’) 250
VI-7-7 [MeNPiPr]Ni(CH2SiMe3) (a1’’) 253
VI-7-8 [MeNPiPr]Ni(CH2SiMe3) (C6H6) (a2) 256
VI-7-9 [MeNPiPr]Ni(CH2SiMe3)(C6H6) (a2’) 259
VI-7-10 [MeNPiPr]Ni(2,4-Lutidine)(Me) (b) 262
VI-7-11 [MeNPiPr]Ni(Me) (b1) 265
VI-7-12 [MeNPiPr]Ni(Me) (b1’) 267
VI-7-13 [MeNPiPr]Ni(Me) (b1’’) 269
VI-7-14 [MeNPiPr]Ni(Me) (C6H6) (b2) 271
VI-7-15 [MeNPiPr]Ni(Me) (C6H6) (b2’) 274
VI-7-16 [CNP]Ni(2,4-Lutidine) (c) 277
VI-7-17 [CNP]Ni (c1) 280
VI-7-18 [CNP]Ni(C6H6) (c2) 282
VI-7-19 [CNP]Ni(C6H6) (c2’) 285
VI-7-20 [MeNPiPr]Ni(Ph)(2,4-Lutidine) (d) 288
VI-7-21 [MeNPiPr]Ni(Ph) (d1) 291
VI-7-22 [MeNPiPr]Ni(Ph) (d2) 293
VI-7-23 [MeNPiPr]Ni(Ph) (d3) 295
VI-7-24 [MeNPiPr]Ni(Ph) (d4) 297
VI-7-25 [MeNPiPr]Ni(pyridine)(CH2SiMe3) (e) 300
VI-7-26 [MeNPiPr]Ni(PMe3)(CH2SiMe3) (f) 303
VI-7-27 [MeNPiPr]Ni(pyridine)(Me) (g) 306
VI-7-28 trans-[MeNPiPr]Ni(PMe3)(Me) (h) 309
VI-7-29 cis-[MeNPiPr]Ni(PMe3)(Me) (i) 312
VI-7-30 [MeNPiPr]Ni(pyridine)(Ph) (j) 315
VI-7-31 [MeNPiPr]Ni(PMe3)(Ph) (k) 318
VI-7-32 [MeNPiPr]Ni(pentafluoropyridine)(Ph) (l) 321
VI-7-33 [MeNPiPr]Ni(2,6-Lutidine)(Ph) (m) 324
VI-7-34 [CNP]Ni(pyridine) (n) 327
VI-7-35 [CNP]Ni(PMe3) (o) 330
VI-7-36 TS1 333
VI-7-37 TS2 336
VI-7-38 TS2’ 339
VI-7-39 TS3 342
VI-7-40 TS4 345
VI-7-41 TS5 347
VI-7-42 TS5’ 350
VI-7-43 TS6 353
VI-7-44 TS7 355
VI-7-45 TS8 358
VI-7-46 Benzene 360
VI-7-47 Tetramethylsilane 360
VI-7-48 Methane 360
VI-7-49 Pyridine 361
VI-7-50 Pentafluoropyridine 361
VI-7-51 2,4-Lutidine 361
VI-7-52 2,6-Lutidine 362
VI-7-53 Trimethylphosphine 362

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