氮烯 (nitrene)是不穩定化合物，本研究嘗試在金屬表面上製備氮
烯並研究其熱化學反應。論文探討銅單晶表面與疊氮及異氰酸酯化合
物(－N=N=N 和－N=C=O)的氣-固相作用，觀察分子釋出N2 或CO
後產生的表面中間體。實驗在超高真空系統中進行，使用程溫脫附質
譜(TPD)，反射吸收式紅外光譜(RAIR)與光電子能譜(XPS)表面分析
技術。參與反應物種則包含benzyl azide (BzN3)，benzyl isocyanate
(BzNCO)與phenyl isocyanate (PhNCO)。Benzyl azide 吸附在Cu(111)
上受熱釋出N2 後，苯環由C 端轉移到N 端產生Ph－N=CH2 (imine)
表面中間體。更高溫時ph－N=CH2 脫氫，苯環再由N 端轉移到C 端
形成η2 (C,N) 側向吸附的ph－C≡N (phenyl nitrile)，並於360 K 由表
面脫附。BzNCO 與BzN3 具等電子官能基，兩者的反應路徑卻不同，
TPD 偵測到toluene (380 K 脫附)，CO2 (410 K 脫附)和HCN (420 K 脫
附)，但表面中間體所呈現的紅外光譜卻與吸附態苯基或甲苯光譜不
吻合。但XPS 能譜的資訊推測BzNCO 在190 K Bz 與NCO 間鍵結斷
裂，Bz 基團由N 端轉移到C 端形成amide 表面中間體。PhNCO 與
BzNCO 均具有苯環與NCO 官能基，可比較兩者反應之相似程度。
RAIR 光譜顯示PhNCO 在170 K 進行環化聚合反應產生二聚體與三聚體，410 K 則觀測到對應acyl amide 物種的紅外光譜，推測PhNCO苯環由N 端轉移到C 端。

Nitrenes are reactive intermediates for many organic reactions, such
as Curtius rearrangement. The thermo- or photochemical- decomposition
of azides or isocyanates was known to generate nitrenes. We investigated
the thermal chemistry of nitrene adsorbed on Cu(111) using benzyl azide
(Bz-N=N=N), benzyl isocyanate (Bz-N=C=O) and phenyl isocyanate
(ph-N=C=O) as precursors under ultrahigh vacuum conditions using
temperature-programmed reaction/desorption (TPR/D), reflectionabsorption
infrared spectroscopy (RAIRS) and X-ray photoelectron
spectroscopy (XPS). Our study shows that despite of the isoelectronic
functionalities (-N=N=N vs. -N=C=O) these molecules undergo different
reaction pathways. For benzyl azide (Bz-N=N=N), the azido group losses
N2 ,and the phenyl group migrates from nitrogen to carbon, forming
surface bound H2C=N-Ph at 210 K. Eventually, H2 elimination and a
carbon-to-nitrogen phenyl shift give the thermally stable ph-CN final
product. XPS reveals that benzyl isocyanate (Bz-N=C=O) rearranges to
form amide intermediate on the surface, which breaks into CO2, HCN
and toluene at 410 K. RAIRs suggests that phenyl isocyanate
(ph-N=C=O) undergoes cyclodimerization, cyclotrimerization and
condensation to remove CO2 at 170 K, and phenyl group shifts from
nitrogen to carbon to produce a metal bound acyl nitrene species
(Ph-(C=O)-N---Cu) at 410 K.

第壹章 前言......................................................................................1
第貳章 實驗設備與藥品處理
2.1 實驗設備............................................................................................4
2.2 藥品……............................................................................................8
第參章 實驗結果與解釋
3.1 Benzyl azide 在Cu(111)上的熱化學反應……………………….10
3.1.1 研究benzyl azide 釋出N2 產生可能的表面中間體...............10
3.1.2 RAIR 光譜推論表面中間體是N-methyleneaniline................12
3.1.3 重排反應：比較苯環轉移與氫轉移的穩定性......................15
3.2 Benzyl isocyanate 在Cu(111)表面的熱化學反應……………......17
3.2.1 Benzyl isocyanate 與benzyl azide 進行不同熱化學反應……17
3.2.2 Benzyl isocyanate 在Cu(111)變溫IR 光譜.............................19
3.2.2.1 相同碳氫結構測得部分的振動光譜相似.………….… .21
3.2.2.2 比較與探討表面中間體的可能性……………………...22
3.2.3 光電子能譜推測amide 的形成……………………………..26
3.3 Phenyl isocyanate 在Cu(111)上的熱化學反應………………......30
3.3.1 高溫m/z 119 訊號推測phenyl isocyanate 產生異構化反應30
3.3.2 phenyl isocyanate 在Cu(111)上進行複雜的熱化學反應…...32
3.3.3 苯環由N 端轉移到C 端形成acyl nitrene….........................34
3.3.4 XPS 能譜推測phenyl isocyanate 與benzyl isocyanate 有相似
的表面中間體............................................................................36
第肆章 討論
4.1 分子內苯環轉移與碳氮雙鍵形成的相關研究…..........................40
4.2 Phenyl isocyanate 在低溫進行自身環化反應................................42
4.3 推測benzyl isocyanate 與phenyl isocyanatee 高溫進行苯基轉移形
成對應的amide................................................................................43
第伍章 結論....................................................................................46
第陸章 參考文獻............................................................................49

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