同碳雙碳烯具有形式上的碳(0)中心，並借助兩側碳烯提供電子達成八隅體穩定。其碳(0)中心上存在兩對相互正交的孤對電子，能作為給電子配位基，展現出雙重配位能力。本論文接續周凱文學長的研究，將咪唑並[1，5-a]吡啶的分子片段引入同碳雙碳烯前驅物的結構設計，與鈀和銥金屬前驅物合成同碳雙碳烯和鈀、銥金屬錯合物。隨後與不同金屬試劑反應形成一系列雙金屬錯合物。 將 6a-Pd、6b-Pd 和 6c-Ir 與第二金屬進行配位反應，三種單核金屬錯合物皆能展現出同碳雙碳烯的典型的偕位配位模式，並形成偕位雙金屬錯合物 (7a-PdCu， 7a-PdIr， 7b-PdIr， 7c-IrCu， 7c-IrAu)。特別的是，6a-Pd、6b-Pd 和 PPh3AuCl；PPh3AgOTf；SMe2AuCl 表現出不同的選擇性反應。首先，發現在 6a-Pd、6b-Pd 系列中可獲得同碳雙碳烯暨異常碳烯鈀金雙金屬錯合物 (8a-PdAu， 8b-PdAu)；與銀金屬反應可獲得碳碳鍵偶聯的單鍵產物 (9a-Pd2， 9b-Pd2)。更令人意外的是，與 SMe2AuCl 反應可獲得碳碳鍵偶聯的雙鍵產物 (10b-Pd2)。我們針對偶聯產物的反應進行了 EPR 的追蹤，在反應的過程中偵測到 EPR 的訊號峰，證實反應過程中生成了順磁性的物質。但在 6c-Ir 的錯合物 (9c-Ir)，卻無法獲得相同的結果，經由實驗結果，我們推論咪唑並[1，5-a]吡啶的結構使得整體配位基的電子共振能力提升，而配位第一個金屬錯合物的氧化性質，會影響反應選擇性。 本研究發現同碳雙碳烯與鈀、銥金屬錯合物兩套系統之反應性差異，探討同碳雙碳烯碳第二對孤對電子在不同配位環境下的電子結構變化，以及其對配位模式與反應選擇性的影響。;Carbodicarbenes (CDC) possess a formal carbon(0) center stabilized by electron donation from two flanking carbene to achieve an octet configuration. The carbon(0) center contains two orthogonal lone pairs， allowing it to act as an electron-donating ligand and exhibit dual coordination ability. Building on the previous work of Kai-Wen Chou， this thesis introduces imidazo[1，5-a]pyridine carbenes into the CDC precursors. These ligands were then reacted with Pd and Ir precursors to synthesize CDC–Pd and CDC–Ir complexes， which were subsequently treated with different metal reagents to afford a series of bimetallic complexes. The reactions of the three mononuclear metal complexes 6a-Pd， 6b-Pd， and 6c-Ir with second metal reagents demonstrate the typical geminal coordination mode of CDC， affording geminal bimetallic complexes (7a-PdCu， 7a-PdIr， 7b-PdIr， 7c-IrCu， and 7c-IrAu). Notably， 6a-Pd and 6b-Pd displayed selective reactivity toward PPh₃AuCl， PPh₃AgOTf， and SMe₂AuCl， affording CDC–aNHC bimetallic complexes (8a-PdAu and 8b-PdAu)， C–C single-bond-coupled complexes (9a-Pd₂ and 9b-Pd₂)， and， unexpectedly， a C–C double-bond-coupled complexe (10b-Pd₂)， respectively. EPR signals were detected during the coupling reaction， suggesting the formation of paramagnetic species. However， 6c-Ir showed different reactivity， affording 9c-Ir instead. Based on these experimental results， we propose that the imidazo[1，5-a]pyridine framework enhances the electronic delocalization ability of the ligand， while the redox properties of the initially coordinated metal center can influence reaction selectivity. This study reveals the reactivity differences between CDC–Pd and CDC–Ir complexes， and investigates how different coordination environments affect the electronic structure of the second lone pair at the carbon (0) center， as well as its influence on coordination modes and reaction selectivity.
