臺灣博碩士論文加值系統

我們利用密度泛函理論(DFT)搭配天然鍵性論(NBO)分析法對過渡金屬羰基錯合物M(CO)42+、M(CO)3Lq[M=Ni2+, Pd2+, Pt2+；L＝F-, Cl-, Br-, H2O, CN-, NH3, NMe3, PMe3, P(OMe)3, PF3]之CO 2π及碳上的孤對電子(5σ)的電子雲密度進行探討，並由E(2)值分析得知金屬回饋鍵結趨勢。
研究中我們發現，在M(CO)42+中CO 2π電子雲密度的大小除了必須考慮金屬d軌域與CO 2π軌域有交互作用外，相鄰碳上的孤對電子(5σ)或金屬碳鍵鍵結電子與CO 2π亦有頗為可觀的交互作用，扣除了這種次要的交互作用後的錯合物M(CO)42+之CO 2π電子雲密度的大小依序為5d＞4d＞3d，也就是第10族過渡金屬的π-回饋鍵結趨勢皆為Pt＞Pd＞Ni。
根據反位影響(trans influence)理論，由反位LP(C)上的[5σ]值去推測出這些配位基的σ-donor能力依序為P(OMe)3＞PMe3＞CN-＞Br-＞Cl-＞F-＞NMe3＞NH3＞H2O，此結果與無機教科書上所提配位基的σ-donor 能力大小順序完全符合，可證明此理論計算方法是具有可信度的。
更有意義的是我們以NBO方法對M(CO)3L2+ [L= PF3, P(OMe)3, PMe3, NMe3]進行研究，顯示出主要接受金屬回饋鍵結的軌域為σ*P-Y( P-Y的σ反鍵結軌域)，並且以取代基中σ*P-Y鍵結極化(polarized extent)的情形及重新混成後σ*P-Y中的p-orbital character的變化量來判斷這些配位基的p back-donation能力大小依序為PF3＞P(OMe)3 > PMe3 > NMe3。

We studies of CO [2p] and LP(C) [5s] in group 10 transition-metal carbonyl complexes M(CO)42+、M(CO)3Lq [M=Ni2+, Pd2+, Pt2+；L＝F-, Cl-, Br-, H2O, CN-, NH3, NMe3, PMe3, P(OMe)3, PF3] by NBO analysis.
This is a subsequent study to cis 5s(CO)2p(CO) hyperconjugation observed in 6B M(CO)6. We have found this BOBO donor-acceptor interaction, in the order 3d>>5d>4d similar to that found in M(CO)6, but considerably smaller than in 6B M(CO)6. Therefore, the net result of 2p population originally in the order 3d<4d<5d .
We have then evaluated the term “trns-influence” in M(CO)3L [M=Ni2+, Pd2+, Pt2+；L＝F-, Cl-, Br-, H2O, CN-, NH3, NMe3, PMe3, P(OMe)3]by analyzing [5σ]. The well-known sequence, P(OMe)3＞PMe3＞CN-＞Br-＞Cl-＞F-＞NMe3＞NH3＞H2O , has been found and supplies another merit of the NBO method .
More significantly, the antibonding BO, s*P-Y plays a more important role than the 3d-AO of P-atom. The p-accepting capabilities of PF3, P(OMe)3, PMe3, depend on the polarized extent of PY (Y= C, O or F) bonding and the 3p-atomic orbital characters. Based on this rehybridization argument, the sequence of p-back-donation strengths is PF3＞P(OMe)3 > PMe3.

摘要............................................................................................................................................I
ABSTRACT.............................................................................................................................II
目錄.........................................................................................................................................III
表目錄.....................................................................................................................................IV
圖目錄......................................................................................................................................V
重要的英文縮寫和其中文譯名..............................................................................................VI
第一章 緒論..............................................................................................................................1
第二章 理論背景......................................................................................................................3
2-1 理論計算原理.............................................................................................................3
2-1.1薛丁格(Schrödinger)波方程式12......................................................................4
2-1.2分子軌域理論(Molecular orbital theory)13,14...................................................5
2-1.3 基底集合(Basis set)15......................................................................................6
2-1.4 密度泛函理論(Density Functional Theory)9...................................................9
2-1.5、NBO分析法10..............................................................................................12
2-2 錯合物之鍵結模型...................................................................................................17
2-3 雲散效應(nephelauxetic effect)25,26,27......................................................................20
2-4 NMR偵測金屬羰基錯合物之CO 2π電子雲密度1,6,28...........................................21
2-5 反位影響(trans influence)41......................................................................................26
第三章 計算過程及所選擇之計算方法................................................................................27
3-1 原始計算流程...........................................................................................................27
3-2 計算過程與分法.......................................................................................................29
第四章 結果與討論................................................................................................................31
4-1 計算方法之探討.......................................................................................................31
4-2 金屬羰基錯合物M(CO)42+之回饋鍵結...................................................................32
4-3 M(CO)3Lq [M=Ni2+, Pd2+, Pt2+]金屬回饋鍵結與反位影響之探討...............38
4-3.1 由反位CO的[2π]值來探討回饋鍵結現象...................................................38
4-3.2 由反位碳上的孤對電子[5σ]值來探討反位影響現象.................................39
4-4 M(CO)3L2+ [L= PF3, P(OMe)3, PMe3, NMe3]金屬回饋鍵結之探討.......................41
4-4.1 以NBO二極微擾能量[ E(2)值]分析配位基L..............................................41
4-4.2 NBO研究配位基中σ*P-Y鍵結極化及重新混成的變化情形61...................42
4-5 M(CO)3X+ [M= Ni2+, Pd2+, Pt2+ ; X-=F-,Cl-,Br-]金屬回饋鍵之探討........................45
第五章結論..............................................................................................................................48
附表 NBO資料錯合物M(CO)3Lq中以CO π*為Accepting BO之主要交互作用.................71
參考文獻.................................................................................................................................77
III

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