有鑑於表面化學對碳烯(carbene ) 研究指出有自偶合
(coupling)與插入(insertion)反應，嘗試在表面上製備nitrene 分子並研究是否有進一步反應發生，此一nitrene 與金屬有鍵結關係的結構稱做Imido 物種，有M=N-R 與M≡N-R 兩種形式，已知表面化學研究中，尚未見文獻有Imido 表面物種的生成與鑑定報導。我們在超高真空環
境下，以azidotrimethylsilane((CH3)3Si-N=N=N; TMSN3)疊氮化合物吸附於Cu(111)表面進行研究。利用程溫脫附實驗(TPD)發現N2 離去，反射式吸收紅外線光譜測得CH3 伸縮振動信號強度增加並有一新吸收峰產生，配合密度泛函理論計算出IR 頻率與光譜比對指認為生成imido 物種之Si-N 伸縮振動。TPD 在520 K 偵測到TMSNH2 胺類化合物與甲烷脫附，推測為Si-C 斷鍵後在表面產生甲基，再分解C-H鍵提供imido 氫化的來源。為進一步確認，以熱燈絲裂解D2 在表面產生氘原子，並偵測到氘化生成的TMSND2 產物。而以同步輻射光源針對N(1s)，Si(2p)與C(1s)能階進行X 光光電子能譜分析，升溫至490K 時，氮、矽與碳的信號均大幅下降，對應TMSNH2 胺分子的脫附。低溫XPS 則發現有向低束縛能化學偏移的N 訊號(395.8 eV)，DFT 電荷分析得知表面imido 結構中氮原子比nitride(M≡N)(396.2 至398.2 eV)
物種更具負電性，得以解釋上述低束縛能N 訊號是緣自imido 的氮，證實imido 物種可由疊氮化合物TMSN3 為前驅物在Cu 表面熱分解生成。800K 的XPS 數據顯示表面有氮化矽(Si3N4)物種，揭示此一系統研究的應用層面。
為釐清Imido 物種被氫化產生胺類化合物過程中氫來源的可能性，以TMS 與疊氮官能基隔著CH2 的TMSCH2N3 分子做進一步研究，意外發現此分子在表面上由於加熱脫附N2 與H2 分子，並於280K 生成TMSC≡N 產物，後續以TMSC≡N 分子進行研究發現TPD 碎片與此產物相符而得到驗證。以TMSC≡N 所進行之實驗由TPD 說明高溫410K 脫附為具有back-π bonding 鍵結之同分異構物TMSN≡C 分子，特徵為寬的TPD 脫附峰。至此，展開對TMSC≡N 異構化反應的探討，該反應特殊之處在於TMS 為一相當大的基團，卻能在表面上進行異構化從碳端(TMSC≡N)轉移至氮端(TMSN≡C)，RAIRS 實驗與DFT 計算指出異構化反應前後最大特徵的改變為氰基的伸縮振動νC≡N，160K 變量IR 與XPS 實驗顯示隨TMSC≡N 量增加該分子會被消耗並轉換為TMSN≡C，推測此反應為分子間反應，而800K 的XPS 與IR實驗對照說明有生成Isocyanide 的聚合物polyisocyanide。

In the organometallic chemistry, the imido complexes are an interesting species because it of their rich reactivity. Imido has two forms, where M=N-R form is nucleophilic and M≡N-R form is elctrophilic. The
thermo- or photochemical- decomposition of metal azido complexes is known to result in the formation of the corresponding metal nitride(M≡N) or imido complexes. These reactions are oxidative cleavage type. As far as we know, imido species have not been generated on metal surfaces; therefore, we attempt to use the azidotrimethylsilane((CH3)3Si-N3 ; TMSN3) as precursors to produce imido species(TMSN=Cu) by N2 extrusion mechanism on Cu(111). The process was explored by a combination of temperature-programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and X-ray photoemission spectroscopy (XPS) techniques. In addition, density functional theory (DFT) calculations were conducted to obtain the optimized geometries
for the various surface intermediates. The computed IR spectra facilitated the vibrational mode assignments. TPD spectra show that TMSN=Cu was
hydrogenated to the TMSNH2 amine product around 520 K. We propose that the hydrogen source is adsorbed methyl groups, invoking the cleavage of the Si-C bond. TMSCH2N3 molecule was also investigated. In this case, N2 and H2 molecules were found to desorb around 260 K and 320K. A novel TMSC≡N product was observed around 280K. We
suggest it is a result of the metathesis reaction from ethylidyne (TMSC≡Cu) and nitride(N≡Cu) species. The TMSC≡Cu species are produced by double α-hydride elimination of TMSCH2-Cu groups. The
N≡Cu may be generated by the thermaldecomposition of copper azide(N=N=N-Cu). RAIRS reveal that there are three kinds of azido vibrations,where the higher frequency is assigned to the N=N=N-Cu species. This product is verified by the TPD of adsorbed TMSC≡N molecule. Intriguingly, the thermal chemistry of TMSC≡N molecule indicates that
the isomeric molecule TMSN≡C could be formed around 210 K, evidenced by a notable change in the RAIRS. The higher frequency νC≡N of TMSC≡N transforms into a lower frequency νC≡N for TMSN≡C. The coverage-dependent studies of RAIRS and XPS performed at 160 K surface temperature show that the isomerization may be intermolecular. The back-π bonded TMSN≡C molecule is desorbed
around 410 K. XPS and RAIRS at 800 K show that isocyanide could polymerize to polyisocyanide, with an imine structure, and the characteristic C≡N stretching mode disappeared.

第壹章 緒論……………………………………………… 1
第貳章 實驗部分…………………………………………. 5
第參章 結果與討論
3.1 TMSN3 在Cu(111)表面的熱化學反應
3.1.1 由IR 光譜與DFT 計算比對推測初始疊氮分子化學吸附型態..……………………………………………… 8
3.1.2 熱反應釋出N2 分子的TPD 證據………………. 11
3.1.3 TMSN3 在Cu(111)變溫IR 光譜………………13
3.1.4 氫化產物TMSNH2 生成的TPD 證據…………15
3.1.5 在Cu(111)上生成Imido(TMSN=Cu)物種的證據
3.1.5.1 Imido 物種的DFT 計算與IR 指認……………17
3.1.5.2 Imido 與Nitride(N≡Cu)物種生成的XPS 證據..19
3.2 氫的來源與氫化Imido 物種的證據
3.2.1 副產物CH4 的生成與CH3I 在Cu(111)熱反應之TPD 比較…………………………………………………23
3.2.2 Imido 物種的氘化反應…………………………24
3.2.3 Imido 物種與表面氫原子的DFT 優化計算… 26
3.2.4 TMSN=Cu 物種Si-C 鍵斷鍵的可行性
3.2.4.1 電荷分析、Hiyama coupling 反應與XPS 的變化說明Si-C鍵斷裂………………………………………27
3.2.4.2 生成Si3N4 的XPS 證據………………………31
3.2.4.3 Cu(111)上氫來源的推論與假設………………32
3.3 TMSCH2N3 在Cu(111)上的熱化學反應
3.3.1 TMSCH2N3 在Cu(111)上的TPD
3.3.1.1 N2 與H2 的脫附………………………………34
3.3.1.2 產物TMSC≡N 脫附……………………………36
3.3.2 TMSCH2N3 在Cu(111)熱反應的IR 光譜與DFT 計算…………………………………………………….39
3.3.3 TMSCH2N3在Cu(111)熱反應的XPS…………43
3.4 TMSC≡N 在Cu(111)上的熱化學反應
3.4.1 TMSC≡N 異構化生成TMSN≡C 的TPD 證據…45
3.4.2 由IR 實驗說明異構化現象是由分子間作用產生..50
3.4.3 XPS 説明TMSNC 在Cu(111)的不同鍵結形式…54
3.5 生成Si-F 鍵的反應研究
3.5.1 TMSN3 和CF3I 共吸附實驗的TPD 結果……61
3.5.2 TMSCH2N3和CF3I 共吸附實驗的TPD 結果…64
第肆章 結論………………………………………… 66
第伍章 文獻資料………………………………………71

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