200406415 (1) 玖、發明說明 相關申請案 本申請案爲申請於2002年6月12日之美國臨時申請 案第60/388,054號及申請於2002年6月12日之美國臨 時申請案 6 0/3 8 7,998號的利益，該等揭示以引用之方式 合倂本文中。 【發明所屬之技術領域】 本發明有關與液態環戊二烯基三甲基鉑化合物、一種 從其製備薄膜、塗料或粉末之方法及一種製備有機金屬化 合物之一釜方法。 【先前技術】 化學蒸氣沈積法被使用於在半導體的製造或加工期間 於基材例如晶圓或其他表面上形成物質的薄膜。在化學蒸 氣沈積法中，化學蒸氣沈積先質（也已知爲一種蒸氣沈積 化合物）被熱、化學、光化學分解或被電漿活化，以形成 一種具有所要組成物之薄膜。例如，氣相化學蒸氣沈積先 質可與一種加熱到高於先質的分解溫度的溫度之基材接觸 ’以在基材上形成金屬或金屬氧化物薄膜。 較佳，化學蒸氣沈積先質在化學蒸氣沈積法之條件下 爲揮發性、熱可分解和能夠產生均勻薄膜。在以化學蒸氣 沈積法製備薄膜中，在室溫爲液態的先質時常是較佳的。 環戊二烯基三甲基鉑化合物是非常有希望的鉑（Pt ) (2) (2)200406415 化學蒸氣沈積先質。化學蒸氣沈積法爲一種將金屬薄膜沈 積在表面上的技術。雖然化學蒸氣沈積先質通常較佳爲液 態，二種最可利用鉑種類，母錯合物（環戊二烯基）三甲 基鉑（mp = 1 09 °C )和（甲基環戊二烯基）三甲基鉑（mp = 3〇C)皆爲固體（Xue 等人 J.AM.Chem.Soc 1 989，3, 8 7 7 9 )。液態先質在大部份情形下於輸送且可產生更一致 的蒸發（也就是，固體可改變產生均勻揮發性之表面積、 粒子大小和結晶性）。 液態環戊二烯基三甲基鉑錯合物（乙基環戊二烯基） 三甲基鉑已揭示在美國專利第5,929,267號中，其中其被 用以形成鉑薄膜。化合物以1 H NMR和CH分析定性。包 括熔化（< -7 8 °C )，密度（· 1 · 5克/公分3 )，和黏度（ 〜5 cP )的評估。痕量金屬分析指示低ppm範圍的雜質。 TG-DTA指示約〇%非揮發性殘餘物。蒸氣壓於50-55°C 發現爲ϋ · 3托。該化合物被報告爲對空氣和水，·以及高 至150°C之溫度穩定（雖然沒有提出半生期數據）。然而 ，此先質從碘三甲基鉑的產率爲中等的5 1 %。 亦’沒有揭示以大量基礎合成有機金屬鉑化合物。環 戊二烯基三甲基鉑錯合物已經從Pt ( IV )(例如， K2PtCl6 )和Pt ( π)(例如，K2ptCi4)來源合成。然而 ’兩條路徑皆經由通式[XPt ( CH3 ) 3]4 ( X =鹵化物（ 例如I))的Pt ( IV )三甲基種類進行（參見圖1，路徑 A )。此四聚物可藉由加入鹵化物置換試劑例如銀鹽（例 如’三氟甲烷磺酸銀）增加反應性。四聚物種類的單離通 -5- (3) (3)200406415 常是經由萃取、沈澱、磨碎和過濾達成。然後此四聚物化 合物可用於形成許多其他包含三甲基鉑的化合物（包括該 等環戊二烯基分子的部分）。沒有藉由從 K2PtCl6或 K2PtCl4合成環戊二烯基三甲基鉑錯合物而沒有如上述所 討論之單離中間產物的直接路徑之嘗試被揭示。 在以化學蒸發沈積法形成薄膜之發展方法中，仍持續 需要較佳在室溫爲液態、具有較高蒸氣壓和可形成均勻薄 膜的化學蒸氣沈積先質。因此，持續存在發展的新穎化合 物和探討其作爲薄膜沈積的化學蒸發沈積先質的可能性之 需要。因此在先前技藝中希望提供一種液態形式且可以高 產率製備之化學蒸發沈積先質，例如，液態環戊二烯基三 甲基鉑先質。 亦，在該技藝中提供一種具有顯著鉑回收之可比例放 大地製備有機金屬鉑化合物的方法將會是一種顯著之進步 。進一步地，在該啦藝中使用一步驟方法合成機金屬鉑化 合物的方法，其中所有的操作在單一容器中進行，及其至 此族化合物不需要單離中間產物錯合物將會是一種顯著之 進步。 【發明內容】 發明槪述 本發明部份係有關選自（異丙基環戊二烯基）三甲基 鉑和（第三丁基環戊二烯基）三甲基鉑之液態環戊二烯基 三甲基鉑化合物。本發明也部份有關一種藉由分解選自（ -6 - (4) (4)200406415 異丙基環戊二烯基）三甲基鉑和（第三丁基環戊二烯基） 三甲基鉑之環戊二烯基三甲基鉑化合物先質製備薄膜、塗 料或粉末之方法，藉此產生薄膜、塗料或粉末。本發明進 一步部份係有關一種製備有機金屬化合物之一釜方法，其 包含在足以產生該有機金屬化合物之反應條件下使金屬來 源化合物、烷化劑和烴或含雜原子之化合物例如（環戊二 烯基化合物）反應。 本發明有幾個優點。例如，本發明的方法可使用於產 生具有不同化學結構和物理性質的有機金屬化合物先質。 該方法可用於製備有機金屬化合物，例，例如，環戊二烯 基三甲基鉑化合物。本發明的方法可比例放大地製備有機 金屬鉑化合物且具有顯著鈾回收。該方法特別適合於比例 放大地製備，因爲可使周容易應用於製造廣泛範圍的產物 之相同設備、一些相同的試劑和方法參數進行。該方法提 供爲一種使用一步驟方法之有機金屬化合物的合成，其中 所有的操作在單一容器中進行，及其至此族化合物不需要 單離中間產物錯合物。 發明之詳細說明 如上所示，本發明部份係有關一種製備薄膜、塗料或 粉末之方法。該方法包括分解至少一種環選自（異丙基環 戊二Μ基）三甲基鉑和（第三丁基環戊二烯基）三甲基鉑 之環戊二烯基三甲基鉑化合物先質的步驟，藉此產生薄膜 、塗料或粉末，如進一步描述在下文者。 -7 - (5) (5)200406415 本發明也部份有關一種製備有機金屬化合物的‘ 一釜， 方法’其促進比例放大及鉑回收兩者。與先前技藝比較沒 有損失產率，本發明避免產生勞工密集和廢物的物質操作 例如萃取之。此本發明的方法也省略一般中間產物的形成 和單離，和減少實質上需要之包括腐蝕的HC1材料（例如 ’化學I式劑’玻璃器具）之數量。此外，因爲所有轉變在 一個容器中發生直到單離（經由昇華/蒸餾）最後產物， 所有其他鉑化合物（例如，副產物）被限制在一個位置。 因爲鉑是一種昂貴的金屬，所循環反應殘餘物以回收殘留 鉑爲一種經濟上的優點，及‘一釜，方法更有益於這個步驟 。產物產率可在從約6 0到9 9 %或更大，較佳從約7 5到 99%或更大，和更佳從約80到99%或更大的範圍。 本發明的方法以許多方式提供料想不到的優點。使用 促進比例放大及鉑回收兩者之簡化一釜合成流程，此從 K2PtCU之材料的產率爲85-90%。化合物爲一種液體，不 像（ΪΜ戊一細基）二甲基鉑和（甲基環戊二燒基）三甲基 鉑。考慮從KdtCU合成碘三甲基鉑之產率爲65%，直接 與上述乙基環戊二烯基的製備比較將調整至8 5 -90 %對43 %。封於昂貝物寊例如銷’此兩倍增加爲一*顯著的優點。 此外，乙基環戊二烯可以9 7 %純度二聚物商品利用，因 此需要裂解和分餾以除去未經取代之環戊二烯，接著去w 子化法。類似的異丙基取代之配位體可以> 99%純度之納 鹽利用。 (異丙基戊一烧基）二甲基銷爲一'種黃色液體（ -8- (6) 200406415 mp = - 36°C ，bp = 122°C 於 5 托，d = 升於2 4 °C，黏度=2 · 7 c P於3 0 °C )。化合物 也就是，熱穩定性）於1 5 0 °C爲約〇 · 5小時。 暴露於空氣，顏色確實慢慢地變暗，所以需要 下。純度以 GC-MS(>99.5%) ，】HNMR( TGA(>99.5%)，和 ICP-MS(>99.9%)測 本發明進一步部份係有關選自（異丙基環 三甲基鉑和（第三丁基環戊二烯基）三甲基鉑 質。此液態鉑先質可呈現優於目前可利用之先 成本優點。該等液態鉑先質可藉由先前技藝已 法製備或藉由本發明的一爸方法製備。較佳， 鉑先質藉由本發明的一釜中方法製備，該方法 產生該液態鉑先質化合物之反應條件下使鉑金 物' 烷化劑和環戊二烯基化合物反應。 如本文所示，本發明包括一種製備有機金 一釜方法，其包括在足以產生該有機金屬化合 件下使金屬來源化合物、烷化劑和烴或含雜原 例（例如環戊二烯基化合物或似環戊二烯基化 。本發明的方法能夠比例放大地製備有機金屬 具有顯著鉑回收。該方法特別適合於比例放大 爲可使用容易應用於製造廣泛範圍的產物之相 些相同的試劑和方法參數進行。該方法提供一 驟方法之有機金屬化合物的合成，其中所有的 容器中進行，及其至此族化合物不需要單離中 1 .43克/毫 的半生期（ 如果化合物 儲存在氮氣 > 99% )， 量。 戊二烯基） 之液態鉑先 質的效能及 知的習用方 本發明液態 包括在足以 屬來源化合 屬化合物之 物之反應條 子之化合物 合物）反應 鉑化合物且 地製備，因 同設備、一 種使用一步 操作在單一 間產物錯合 -9- (7)200406415 物。 金 屬化合 屬來源 (其中 );和 金 要爲提 有機金 反應混 毫莫耳 法法應 烷 。作爲 RMgX 爲用於 烷 欲使用 化合物 物的大 更大的 本 烴類、 類、聚 屬來源化合物可選自該技藝已知的廣泛多樣之含金 物。作爲實例的金屬包括鉑、鈀和鎳，較佳鉑。金 化合物較佳爲任何的銷金屬化合物，更佳M2PtX6 Μ爲驗金屬、驗土金屬、銀或錢，和X爲鹵化物 最佳 K2PtCl6。 屬來源化合物的濃度可在廣泛的範圍改變，且只需 供欲使用之所需金屬濃度和將會供給至少本發明的 屬化合物所需之金屬量的基礎之最小量。一般，視 合物的大小而定，在約1毫莫耳或更少到約〗〇〇〇 或更大的範圍之金屬來源化合物濃度，對大多數方 是足夠的。 化劑可選自該技藝已知的廣泛多樣之含金屬化合物 實例的院化劑包括RAuLi (其中 R爲院基）； (其中R爲院基，X爲鹵化物）；和RLi (其中R 三甲基鉑合成的CH3 )。 化劑的濃度可在廣泛的範圍改變，且只需要爲提供 之所需ibt基濃度和將會供給至少本發明的有機金屬 所需之烷基量的基礎之最小量。一般，視反應混合 小而疋’在約1毫莫耳或更少到約I 〇 〇 〇毫莫耳或 箪E圍之院化劑濃度，對大多數方法法應是足夠的。 發明的方法中所使用的溶劑可爲任何飽和及不飽和 方烴類、芳族雜環類、鹵烷類、矽烷基化烴類、醚 醚、硫醚類、酯類、內酯類、醯胺類、胺類、聚胺 -10- (8) (8)200406415 類、腈類、矽酮油類、其他非質子溶劑、或一或多種上述 的混合物；更佳己烷類、戊烷類、或二甲氧基乙烷類；和 最佳乙醚或THF。可使任何用的不會不適當地不利干擾所 要之反應之適當溶劑。如果需要可使用一或多種不同溶劑 的混合物。所使用之溶劑的量對本發明並不重要且只需要 爲足以溶解反應混合物中的反應成分之量。一般，溶劑的 量可在基於反應混合物起始物質的總重量之從約5重量％ 高至約99重量％或更多的範圍。 反應條件例如溫度、壓力和接觸時間也可改變很大且 任何該等條件之適當組合可使用在本文中。反應溫度可爲 任何一種上述溶劑的回流溫度，和更佳在約-1 〇 〇 °C到約 2 5 °C之間，和最佳在約〇 °C到約2 5 °C之間。正常反應在室 壓下進行及接觸時間可從約幾秒或幾分鐘改變到幾小時或 更大。反應物可以任何順序加至反應混合物或組合物。 反應停止劑可選自該技藝已知的廣泛多樣之化合物。 作爲實例的使用於本發明之反應停止劑包括鹵烷類、酮類 、醇類、水、礦物酸類、有機酸類、羧酸類；且更佳卜 溴基-2-氯乙烷，卜溴基-2-氟乙烷，甲烷，且最佳；!，2_二 溴乙烷。 反應停止劑的濃度可在廣泛的範圍改變，且只需要爲 製備本發明的有機金屬化合物所需之最小量。一般，視反 應混合物的大小而定，在約1毫莫耳或更少到約1 0 0 0毫 莫耳或更大的範圍之反應停止劑濃度，對大多數方法法應 是足夠的。 -11 - (9) (9)200406415 藉由本發明方法製備之有機金屬化合物可以式lm( R) 3表示’較佳LPt(R) 3，其中l爲烴或含雜原子基， 其可選自碳水化合物類、參（吡唑基）硼酸鹽類、3種吡 D疋類、二吡啶類、三吡啶類、3種膦類、二膦類、三膦類 3種fe：類、一胺類、三胺；更佳P_二酮酸鹽類（ diketonate) ’ R爲直鏈或支鏈烷或矽烷基，及μ爲一種 選自鉑、絶和鎳的金屬。較佳、L選自五合（pentahapt0 )、無_、單…二…三_、四…五取代之環戊二烯基、茚 基、環和非環烯丙基類；R爲甲基，及Μ爲鉑。更佳，L 選自環戊二烯基和似環戊二烯基的化合物。似環戊二烯基 分子部分的例子包括環-烯烴、例如環己二烯基、環庚二 烯基、環辛二烯基環、雜環類、芳環類，例如經取代或未 經取代之次苯甲基（b e n z e n y 1 )，和其他，如該技已知的 〇 提供L之烴或含雜原子基化合物的濃度可在廣泛的範 圍改變’且只需要爲提供欲使用之所需L濃度和將會供給 至少本發明的有機金屬化合物所需之L量的基礎之最小量 。一般，視反應混合物的大小而定，在約1毫莫耳或更少 到約1 0 0 0毫莫耳或更大的範圍之L濃度，對大多數方法 法應是足夠的。 當環戊一嫌基化合物使用在反應時，環戊二燃基（或 經取代之類似物）遞送可藉由非去質化之二烯（例如，環 戊二烯）發生，較佳環戊二烯基化合物的鋰、鉀、銳、錢 、鈣、或鎂鹽。可以固體或者以與上述任何溶劑的溶液， -12- (10) (10)200406415 較佳-1 ·· 2 Μ溶液的鈉鹽加入。 在本發明方法中所使之攪拌時間可在所有步驟的從約 〇· 1到約200小時，更佳烷基化（例如，甲基化）的從約 2到約1 〇 〇小時，停止反應的從約2到約7 2小時，和環 戊二烯基加入的從約0 · 1到約4 8小時範圍。更佳，攪拌 時間可從甲基化的約2到1 6小時，停止反應的2到1 6小 時’和環戊二烯基加入之的0.1到1小時的範圍。 對於藉由本發明方法製備的有機金屬化合物，純化作 用可經由再結晶作用，更佳經由反應殘餘物的萃取（例如 ’己烷）和色層分析法，和最佳藉由昇華和蒸餾發生。 熟習該項技術者應知可對本文描述詳細之方法進行很 多的變化，而沒有離開如更特別定義在下列申請專利範圍 內之本發明的範圍或精神。 可兩以定性藉由上述合成方法形成之環戊二烯基三甲 基鉑化合物的技術之例子包括（但不限制於）分析色相色 層分析法，核磁倥共振，熱重量分析，誘發偶合之電漿質 譜分析法，蒸氣壓和黏度測量。 上述環戊二烯基三甲基鉑化合物先質之相對蒸發壓、 或相對揮發度可藉由該技藝已知的熱重量分析技術測量。 也可測量平衡蒸氣壓，例如從封閉的容器抽空所有的氣體 ’之後將化合物的蒸汽導至容器中及如該技藝已知的測量 〇 本文所述之環戊二烯基三甲基鉑化合物先質在室溫爲 液恶且適合於就地製備粉末和塗料。例如，液態環戊二録 -13- (11) 200406415 基Η甲基鉑化合物先質可塗覆至基材，然 解該先質的溫度，藉此在基材上形成金屬 層。將液態先質塗覆到基材可藉由油漆、 由其他該技藝已知的技術。加熱可在烤箱 由電加熱基材，或藉由其他該技藝已知的 塗料可藉由塗覆環戊二烯基三甲基鉑化合 熱且分解，藉此形成第一層，接著以至少 或不同的其他塗料覆，和加熱而獲得。 例如上述之液態環戊二烯基三甲基鉑 霧化及噴霧在基材上。可使用之霧化和噴 噴嘴，噴霧器和其他，爲該技藝已知的。 在本發明較佳具體實施例中，環戊二 合物，例如上述，可使用在形成粉末、薄 沈積技術中。化合物可以單一來源先質使 更多其他的先質一起使用，例如，與藉由 他有機金屬化合物或金屬錯合物所產生的 的方法中也可使周超過一種之環戊二烯基 先質，例如上述。 沈積可在其他氣相成分存在下進行。 實施例中，薄膜沈積在至少一種非反應性 進行。非反應氣體的例子包括惰性氣體， 氦，以及在方法條件下不與環戊二烯基三 質反應的其他氣體。在其他具體實施例中 少一種反應性氣體存在下進行。一些可使 後加熱到足以分 或金屬氧化物塗 噴霧，浸漬或藉 '使用熱槍、藉 方法進行。層化 物先質及將其加 一種與先質相同 化合物先質也可 霧裝置法，例如 烯基三甲基鉑化 膜或塗料之氣相 用或可與一種或 加熱至少一種其 蒸氣。在所給定 三甲基鉑化合物 在本發明一具體 載體氣體存在下 例如，氮、氫、 甲基鉑化合物先 ，薄膜沈積在至 用的反應性氣體 -14 - (12) (12)200406415 包括（但不限制於）聯胺、氧、氫、空氣、富氧空氣、臭 氧（〇3)、氧化氮（N2〇 )、水蒸汽、有機蒸氣和其他。 如該技藝已知的，氧化氣體，例如，例如，空氣、氧、富 氧空氣、0 3、N2 0或氧化有機化合物的蒸氣之存在，有利 於金屬氧化物薄膜的形成。 可進行本文所述之沈積方法以形成包括單一金屬之薄 月吴、粉末或塗料（例如，P t -薄膜），或包括單一金屬氧 化物的薄膜、粉末或塗料。也可沈積薄膜、粉末或塗料混 合’例如混合之金屬氧化物薄膜。混合之金屬氧化物薄膜 可藉由，例如，使用幾種有機金屬先質（其至少一種選自 上述環戊二烯基三甲基鉑化合物）形成。 可進行氣相薄膜沈積以形成所要厚度的薄膜層，例如 ’在從約1奈米到1毫米以上的範圍。本文所述之先質特 別可使用於製備薄膜，例如，具有約1 0奈米到約1 00奈 米範圍的厚度之薄膜。鉑的薄膜，例如，可被考慮用於製 造金屬電極，特別是作爲邏輯之P -通道金屬電極，和作 爲DRAM應用的電容器電極。 該方法也適合於製備層化薄膜，其中至少二層中的相 或成分不同。層化薄膜之例子包括金屬-絕緣體-半導體， 和金屬-絕緣體-金屬。 在一具體實施例中，本發明係有關一種方法，其包括 熱、化學、光化學或藉由電漿活化作用分解上述環戊二烯 基Η甲基鉑化合物先質之蒸氣的步驟，藉此在基材上形成 薄膜。例如，藉由在室溫爲液體的化合物所產生之蒸氣與 -15- (13) (13)200406415 具有足以引起環戊二烯基三甲基鉑化合物分解且在基材上 形成薄膜的溫度之基材接觸。 該等環戊二烯基三甲基鉑化合物先質可使用於該技藝 已知的化學蒸氣沈積或，更特別地，金屬有機化學蒸氣沈 積方法中。例如，上述環戊二烯基三甲基鉑化合物先質可 用於大氣壓，和低壓之化學蒸氣沈積法中。化合物可用於 熱壁化學蒸氣沈積中，一種其中整個反應容器被加熱的方 法，以及冷或溫壁類型化學蒸氣沈積法，一種其中只有基 材被加熱之技術。 上述環戊二烯基三甲基鉑化合物先質上也可使用於電 漿或光-協助之化學蒸氣沈積法中，其中來自電漿之能量 或電磁能量分別地使用於活化化學蒸氣沈積先質。化合物 也可使於離子束、電子束協助之化學蒸氣沈積法，其中離 子束或電子束分別地指向基材以供應用於分解化學蒸氣沈 積先質之能量。也可使用雷射-協助之化學蒸氣沈積法， 其中雷射光指向基材以產生化學蒸氣沈積先質的光致反應 c 本發明方法可在各種化學蒸氣沈積反應器中進行，例 如’例如，熱或冷-壁反應器，電-協助，光束協助或雷 射-協助之反應器，如該技藝已知的。 在化學蒸氣沈積製製造期間，在室溫爲液態的先質爲 較佳和（異丙基環戊二烯基）三甲基鉑和（第三丁基環戊 二烯基）三甲基鉑具有使他們適合作爲化學蒸氣沈積先質 的性質。 -16- (14) (14)200406415 可藉由本發明方法塗覆之基材的例子包括固體基材例 如金屬基材’例如 A1、N i、T i、C 〇、P t、T a ;金屬$夕化( 物’例如TiSi2、C〇Si2、NiSi2 ;半導體材料，例如Si、 S i G e、G a A s、I η P、鑽石、G a N、S i C ;絕緣體，例如 s i 〇 2 、S i 3 N 4、H f Ο 2、T a 2 0 5、A12 O 3、鈦酸緦鋇（b S T );屏 障材料’例如TiN.、TaN ;或在包括材料組合的基材上。 此外’薄膜或塗料可在玻璃，陶瓷，塑膠，熱固性聚合的 材料上形成，和在其他塗層或薄膜層上形成。在較佳具體 實施例中，薄膜沈積是在使用於電子元件之製造或加工之 基材上。在其他具體實施例中，基材用以支撐在氧化劑存 在下於高溫穩定的低電阻導體或光傳輸薄膜。 可進行本發明方法以在基材上沈積一具有平滑之平坦 表面的薄膜。在一具體實施例中，進行該方法以在用於晶 圓製造或加工之基材上形成薄膜。例如，進行該方法以在 包括特徵例如溝，孔或vias的製圖基材上形成薄膜。此 外’本發明方法也可與晶圓製造或加工中之其他步驟例如 ，光罩、齡刻和其他整合。 化學蒸氣沈積薄膜可沈積至所要的厚度。例如，所形 成的薄膜可小於1微米厚度，較佳少於5 0 0奈米和更佳少 於2 00奈米厚度度。也可製備小於50奈米厚度的薄膜， 例如，具有在約20和約30奈米之間的厚度之薄膜。 上述環戊二烯基三甲基鉑化合物先質上也可使用在本 發明方法中以藉由原子層沈積（ALD )或原子層成核（ ALN )技術形成薄膜，期間基材暴露於先質、氧化劑和惰 -17- (15) (15)¢00406415 性氣體流之交替脈衝中。後來之層沈積技術描述於，例如 美國專利第6,2 8 7,9 6 5號和美國專利第6,3 42,27 7號中。 兩專利的揭示全部以引用之方式合倂在本文中。 例如’在一 A L D循ί哀中’基材以逐步驟方式暴露於 :a )惰性氣體；b )運送的先質蒸氣之惰性氣體；c )惰 性氣體；和d )氧化劑，單獨或連同惰性氣體。一般，每 個步驟可如裝備所允許般短（例如毫米）且只要方法需要 (例如幾秒或分鐘）。一個循環期間可短如毫秒和長如分 鐘。循環可重複從幾分鐘到小時範圍的週期。所產生的薄 膜可爲幾奈米薄或較厚，例如，1毫米（mm )。. 本發明方法也可使用超臨界液進行。目前在該技中爲 已知的使用超臨界液之薄膜沈積方法的例子包括化學液沈 積；超臨界液傳送-化學沈積；超臨界液化學沈積；和超 臨界浸漬沈積。 化學液沈積法，例如，非常適合於製備高純度薄膜和 轉化錯合物表面和高外觀比的充塡。化學液沈積法描述於 例如美國專利第5,7 8 9,027號中。超臨界液體使用於形成 薄膜也在揭述在美國專利第6，5 4 I 2 7 8 B 2號中。兩專利的 揭示全部以引用之方式合倂在本文中。 在本發明一具體實施例中，一加熱之製圖基材暴露於 一或多種環戊二烯基三甲基鉑化合物先質中，在溶劑存在 下，例如接近臨界或超臨界液體，例如，接近臨界或超臨 界C02，溶劑液在約1〇〇〇 psig以上之壓力和至少約30°C 之溫度下提供。 -18- (16) (16)200406415 先質分解而在基材上形成金屬薄膜。反應也從先質產 生有機材料。有機材料藉由溶劑液溶解且容易地從基材除 去。例如藉由使用氧化體，也可形成金屬氧化物薄膜。 在~實施例中，沈積法在罩住一或多個基材之反應室 中進行。基材藉由加熱全整個室而加熱到所需要的溫度， 例如’經由爐。環戊一嫌基二甲基鉑化合物的蒸氣可藉由 例如施用真空到室而產生。對於低沸點化合物，該室爲足 以引起化合物的蒸發之熱。當蒸氣與加熱之基材表面接觸 時’其分解且形成金屬或金屬氧化物薄膜。如上所述，環 戊一嫌基二甲基舶化合物先質可單獨或與一或多種成分， 例如，例如，其他有機金屬先質、惰性載體氣體或反應性 氣體組合使周。 在可用於以本發明方法製備薄膜之系統中，原料可直 接到氣體-摻合歧管以產生供應到沈積反應器（其中進行 薄膜生長）中的方法氣體。原料包括（但不限制於）載體 氣體、反應性氣體、沖洗氣體、先質、蝕刻/淸潔氣體和 其他。方法氣體組成物之精確控制使用質量流控制器、閥 、壓力轉換器，和其他裝置完成，如該技藝已知的。排氣 歧管可遞送離開沈積器之氣體和旁流到真空泵。減輕系統 ’真空泵下流，可用以從廢氣除去任何危險物質。沈積系 統可裝備就地分析系統，包括殘氣分析器，其允許方法氣 體組成物的測量。控制和數據獲得系統可監測各種方法參 數（例如，溫度、壓力、流速等）。 上述環戊二烯基三甲基鉑化合物先質可用於製備包括 (17) (17)200406415 單一金屬的薄膜，例如，Pt-薄膜，或包括單一金屬氧化 物的薄膜。混合薄膜也可被沈積，例如混合之金屬氧化物 薄膜。該等薄膜係例如藉由使用幾種有機金屬先質，其中 至少一種選自上述之環戊二烯基三甲基鉑化合物而製備。 例如’也可藉由使用沒有載體氣體、蒸氣或其他的氧來源 形成金屬薄膜。 藉由本文所述方法形成之薄膜可藉由該技藝已知的技 術性，例如，藉由X光繞射、Augar光譜、X-射線光電子 發射光譜、原子強迫顯微鏡檢查、掃描電子顯微鏡檢查和 在該藝中已知的其他技術。藉由該技藝已知的方法也可測 量薄膜的電姐和熱穩定性。 本發明的各種修正和變化對於熟習該項技術者是顯而 易知的，且應了解該等修正和變化將包含在本申請案的範 圔和申請專利範圍的精神和範圍中。 [實施方式】 實例1 如B 〇 a r d m a η和N em a r k (化學中的核磁共振1 9 9 2， 3 0，4 8 1 )所報告的完成圖1所述之反應，路徑A以合成 其他環戊二烯基鉑合物。在本情形中，利用異丙基環戊二 _鈉產生一種非先前合成之新穎化合物。碘三甲基鉑之合 成的產率爲80% (報告爲89%)。後來（異丙基環戊二 _基）三甲基鉑（一種黃色的液體）的產率爲8 8 %。總 產率（兩步驟）爲70%。 雜 -20- (18) (18)200406415 實例2 完成圖1所述反應，路徑B。所有的玻璃器具烘乾過 夜。配備有攪動棒之2升三頸圓底瓶，安裝隔板加蓋之加 入漏斗，連接到Schlenk管線之真空接管，和隔板。在氮 氣下乾燥之後，短暫移除燒瓶隔板以加入K2PtCl6 ( 41.5 克，8 5 · 5毫莫耳）。系統以氮再沖洗一次。無水的無抑制 劑之四氫呋喃（THF ) (850毫升）壓力轉移至加入漏斗 中和加至燒瓶內。開始攪拌和將黃色漿液冷卻到〇艺。 1.4M甲基鋰的乙醚溶液（500毫升，700毫莫耳）壓力轉 移至加入漏斗內。甲基鋰溶液以致使反應混合物的溫度始 終固定在5 °C以下的速率逐滴加入（經5 - 6小時）。在加 入的開始時必需較慢的加入速率，在2小時之後只有加入 總體積的2 0 %。一旦甲基鋰加入完成，使反應混合物溫 熱到室溫。如繼續攪拌過夜（〜1 6小時）黃棕色懸浮液褪 色至淡黃褐色。懸浮液再次冷卻到〇°C。氮沖洗之1，2-二 溴乙烷（40毫升，460毫莫耳）以致使反應混合物的溫度 始終固定在5 °C以下的速率逐滴加入（經2-3小時）。在 加入的開始時必需較慢的加入速率，在2小時之後只有加 入總體積的20%。使反應混合物於0°C攪拌〜4小時，然 後使溫熱到室溫同時攪拌過夜（〜1 6小時）。在減壓（ 〜〇·1托）和溫和熱（3 0-40 °C )下除去溶劑和過量1,2-二 溴乙烷。固體在真空下留置3小時。棕色殘餘物懸浮在 THF中，且藉由壓力轉移加入異丙基環戊二烯鈉（12.2克 -21 - (19) (19)200406415 ，94毫莫耳）之0·6 M THF溶液（經20-30分鐘）。攪 拌1小時之後，在減壓下除去溶劑，及經由‘短路徑，蒸飽 單離產物以產生87%產率之黃色液‘體。 實例3 完成圖1所述反應，路徑B。所有的玻璃器具烘乾過 夜。配備有攪動棒之三頸圓底瓶安裝隔板加蓋之加入漏4 ，連接到 Schlenk管線之真空接管，和隔板。在氮氣下 乾燥之後，短暫移除燒瓶隔板以加入K2PtCl6 ( 41.5克， 8 5 · 5毫莫耳）。系統以氮再沖洗一次。無水的無抑制劑之 四氫呋喃（THF ) ( 85毫升）壓力轉移至加入漏斗中和加 至燒瓶內。開始攪拌和將黃色漿液冷卻到〇fcC。1 ·4Μ甲基 鋰的乙醚溶液（5 0毫升，7 0毫莫耳）壓力轉移至加入漏 斗內。甲基鋰溶液以致使反應混合物的溫度始終固定在5 °C以下的速率逐滴加入（經3 - 4小時）。在加入的開始時 必需較慢的加入速率，在1小時之後只有加入總體積的 2 0 %。一旦甲基鋰加入完成，使反應混合物溫熱到室溫。 如繼續攪拌3 -4小時之後黃色懸浮液褪色至無色。使反應 攪拌過夜（〜1 6小時）。懸浮液再次冷卻到。氮沖洗 之1，2-二溴乙烷（40毫升，460毫莫耳）以致使反應混合 物的溫度始終固定在5。(：以下的速率逐滴加入（經1小時 )。在加入的開始時必需較慢的加入速率，在1小時之後 只有加入總體積的2 0 %。使反應混合物於〇 °c攪拌〜4小 時’然後使溫熱到室溫同時攪拌過夜（〜1 6小時）。在減 (20) (20)200406415 壓（〜0· 1托）和溫和熱（〜3 〇°C )下除去溶劑和過量ι，2-二溴乙烷。爲了幫助完全除去1，2 ·二溴乙烷，將很少的 THF加至固體殘餘物中和再蒸發。固體在真空下留置3小 時。棕色殘餘物懸浮在T H F中且藉由壓力轉移加入甲基 環戊二烯鈉（由雙蒸餾之甲基環戊二烯和NaH製備）（ 1.0克，10毫莫耳）之1·3Μ THF溶液（經過20-30分鐘 )。攪拌1小時之後，在減壓（〜〇 · 5托）下除去溶劑，及 經由‘短路徑’蒸餾或昇華（報告之昇華溫度：23 t，於 0.0 5 3毫米）單離產物以產生6 5 - 7 5 %產率之白色結晶。 純度：>99.5%，藉由 GC/MS，>99% 藉由 NMR，<0.1 % NVR 藉由 TGA。 實例4 在烷基化步驟中使用甲基鋰和20體積THF之（甲基 環戊二烯基）三甲基鉑的製備 備有磁性攪拌棒、熱電偶、二個均壓加入漏斗及連接 到氣體起泡器的氮/真空管線之5 0 0毫升烤乾四頸圓底燒 瓶中進料六氯鉑酸鉀（1 〇克，2 0 · 5 8毫莫耳）。將系統封 閉和短暫抽氣，然後以氮氣沖洗。重複兩次沖洗循環。使 用微正氮壓（3-5 psi )將無水的無抑制劑之THF ( 2 00毫 升，2 0體積）壓力轉移至加入漏斗內，然後排入燒瓶內 。使用冰/乙醇浴將所得黃色漿液冷卻至〇 °C，然後用氮 沖洗兩次。使用微正氮壓（3-5 psi )將甲基鋰在乙酸中的 溶液（105.5毫升，168.8毫莫耳，8.2當量）壓力轉移至 -23- (21) (21)¢00406415 加入漏斗，然後以2-5毫升部分及〗5分鐘間隔經6小時 加入’同時反應混合物的溫度維持在〜2它和4 〇c之間。在 1小時內最初嫩黃漿液變成黃色/黃褐色。後來各加入甲基 鋰時’黃褐色色調短暫褪色但如反應進行時再產生。甲基 鋰加入的結束時，批次外觀爲淡黃色/黃褐色且混濁的溶 液。使反應混合物慢慢地溫熱到室溫過夜。進一步攪拌 1 4小時之後，批次外觀爲灰白色混濁溶液。反應混合物 冷卻到0 C和經3小時經由加入漏斗慢慢地加入氮沖洗之 1，2·二溴乙烷（10毫升，5.2當量）停止反應。在停止最 初觀察到很多的氣體放出，但是在加入約4毫升的二溴乙 烷之後此放出停止。使反應混合物溫熱到室溫和進一步攪 拌18小時以提供黃褐色混濁的溶液。燒瓶固定在加熱罩 中，安裝短路徑蒸餾頭，和在中等真空（約1 4 0毫米汞柱 )下於3 5 °C蒸餾大部分溶劑。於1 . 5托和3 5 - 4 0 °C除去剩 餘的1,2-二溴乙烷經3小時。無水的無抑制劑THF ( 80 毫升，8體積）加至燒瓶和激烈攪拌所得懸浮液以提供細 固體的棕色懸浮液。MeCpLi在THF/己烷中的溶液[60毫 升，0.3 8 Μ，I. 1當量]經3 0分鐘慢慢地加至懸浮液和所得 混合物在室溫下攪拌1小時。棕色漿液壓力轉移至5 00毫 升乾圓底瓶內和在旋轉蒸發器上在減壓下於2 8 C汽提溶 劑以產生棕色流動發液。無水庚烷（2 0 0毫升’ 2 0體積） 加至漿液及激烈攪拌懸浮液。由於加入庚院’大量固體黏 著至到燒瓶。停止攪拌和使固體沈降。上淸液壓力轉移至 5 00毫升燒瓶內和在旋轉蒸發器上於2 8 -3 5 °C濃縮以產生 -24- (22) (22)200406415 黃棕色油狀殘餘物[7 · 95克]。產物藉由真空蒸餾（0.13托 ，bp 4 6-4 7 °C )純化以提供68.5%產率[4.5克]的標題錯 合物。藉由GC之分析指示92.5% ( AUC广的純度與〇,9 % ( AUC )(甲基環戊二烯基）三甲基鉑和帶有5.8% ( AUC )十二烷污染物來自用以由MeCp單體製備MeCpLi 的正-己基鋰。1H NMR光譜與指定之結構一致。 實例5 在烷基化步驟中使用甲基鋰和10體積的THF之（甲 基環戊二烯基）三甲基鉑的製備 5 00毫升備有磁攪拌棒、熱電偶、均壓加入漏斗及連 接到氣體起泡器的氮/真空管線之乾三頸圓底瓶中進料六 氯鉑酸鉀（1 〇克，2 0.5 8毫莫耳）。將系統封閉和短暫抽 氣，然後以氮氣沖洗。重複兩次沖洗循環。使用微正氮壓 (3-5 p si )將無水的無抑制劑之THF ( 100毫升，10體積 )壓力轉移至加入漏斗內，然後排入燒瓶內。使用冷卻劑 將所得黃色漿液冷卻至0 °C，然後用氮氣沖洗兩次。使用 微正氮壓（3-5 psi )將甲基鋰在乙醚中的_溶液（1〇5.5毫 升，168.8毫莫耳，8.2當量）壓力轉移至加入漏斗，然 後經6小時加入2-5毫升部分中，同時反應混合物的溫·度 維持在0-2 °C之間。關掉冷卻器及使反應混合物慢慢地溫 熱到室溫和攪拌過夜。反應混合物冷卻到〇t：和經2h經 由藉由加入漏斗慢慢地加入氮氣沖洗之丨，2 _二溴乙烷（1 〇 毫升’ 5 ·2當量）停止反應。使反應混合物溫熱到室溫和 -25 - (23) (23)200406415 進一步攪拌過夜以產生黃褐色之混濁溶液。將燒瓶安裝短 路徑蒸餾頭，冷卻劑液設定於4〇 °C，和在中等真空（約 1 4 0毫米汞柱）下於3 5 °C蒸餾大部份溶劑。剩餘的1，2 -二 溴乙烷在1 . 〇托和4 0。(：經2小時進一步除去。無水的無抑 制劑之TB F ( 1 0 0毫升，1 0體積）加至棕色固體殘餘物和 激烈攪拌所得懸浮液以產生細固體的棕色懸浮液。來自漿 液的等分藉由GC之分析指示很少量的二溴乙烷仍存在於 殘餘物中。如上所述進一步蒸餾溶劑，殘餘物懸浮在THF (80毫升，8體積）中且攪拌以生棕色漿液。進一步的 GC分析指示只有痕量之二溴乙烷存在於殘餘物中。 MeCpLi在THF/己烷中的溶液[63毫升，0.36M，1.1當量] 經3 0分鐘慢慢地加至懸浮液和所得混合物在室溫下攪拌 1小時。在減壓下蒸餾大部份THF ( 140毫米汞柱，35°C ，約除去60毫升THF )。無水庚烷（200毫升，20體積 )加至所得棕色漿液中，激烈攪拌懸浮液1小時以萃取產 物。停止攪拌，使固體沈降，和上淸液壓力轉移至5 0 0毫 升燒瓶內。無水THF ( 40毫升）和無水庚烷（160毫升） 加到固體殘餘物，激烈攪拌懸浮液1小時以進一步萃取產 物。合倂上淸液與最初的萃取物及在旋轉蒸發器上於減壓 下除去溶劑以產生黃棕色漿液。無水THF ( 5 0毫升）加 至漿液中，所得棕色溶液轉移到1 00毫升燒瓶和在減壓下 進一步除去溶劑以產生棕色油狀物[1 2 · 5 9克]，產物藉由 真空蒸餾（0.3到0.4托，bp 56-5 7°C ]純化以產生61%產 率[4.0 1克]的標題錯合物。最初單離之無色油狀物在室溫 (24) 200406415 靜置時固化以產生灰白色固體（mp = 29-3 0 °C GC之分析指示純度>99% (AUC)與<0.1% ( 甲基環戊二烯基）三甲基鉑。1Η N MR光譜與指 一致。藉由ICPMS之進一步痕跡金屬分析指示 的所有合倂痕量金屬，因此>99.999%Pt含量。 實例6 在烷基化步驟中使用氯化甲基鎂之（甲基環 )三甲基鉑的製備 5〇〇毫升備有磁攪拌棒、熱電偶、均壓加入 接到氣體起泡器的氮/真空管線之乾三頸圓底瓶 氯鉑酸鉀（1 0克，2 0 · 5 8毫莫耳）。將系統封閉 氣’然後以氮氣沖洗。重複兩次沖洗循環。使用 (3»5 psi )將無水的無抑制劑之THF ( 1 00毫升 )壓力轉移至加入漏斗內，然後排入燒瓶內。使 醇浴將所得黃色漿液冷卻至〇 °C，然後用氮氣沖 使用微正氮壓（3-5 psi)將氯化甲基鎂在TBF (56.3毫升，3·〇 Μ，]68·8毫莫耳，8.2當量） 至加入漏斗’然後經】小時逐滴加到漿液中。使 物慢慢地溫熱到室溫和攪拌過夜。反應混合物冷 和藉由以單一部分慢慢地加入氮氣沖洗之i，2_二 1 〇毫升’ 5 ·2當量）停止反應。使反應混合物溫 和進一步攪拌2 · 5 d。將燒瓶安裝短路徑蒸餾頭 和在中等真空（約〗4 〇毫米汞柱）下於3 5 °C蒸 )。藉由 AUC )( 疋之結構 3.57 ppm 戊二烯基 漏斗及連 中進料六 和短暫抽 微正氮壓 ，10體積 用冰/乙 洗兩次。 中的溶液 壓力轉移 反應混合 卻到0 °c 溴乙烷（ 熱到室溫 及加熱罩 餾大部分 •27- (25) (25)200406415 之溶劑。在1·〇托和40°C經2小時進一步除去剩餘ι，2-二 溴乙烷。無水的無抑制劑之THF ( 8 0毫升，8體積）加至 灰白色固體'殘餘物且懸浮液在室溫下激烈攪拌4小時。 MeCpLi在THF/己烷中的溶液[60毫升，0·38 M，1.1當量 ]經3 0分鐘慢慢地加至漿液中和所得混合物在室溫下激烈 擾泮4小時。所得榮液轉移到5 0 0毫升燒瓶中且在旋轉蒸 發器上除去T H F以產生黃-棕色固體殘餘物。將無水庚烷 (2 0 0毫升）加至殘餘物，但不能夠達成溶解作用。加入 無水TBF ( 200毫升），備有Claisen接管和機械攪拌器 之燒瓶，和懸浮液在室溫下攪拌過夜。上淸液轉移到500 毫升燒瓶，然後在使用1 00毫升燒瓶之旋轉蒸發器上汽提 以產生黃-棕色油狀殘餘物[1 2.8 7克]。藉由於〇 . 2 5到 0.5 0托（b p 5 5 °C )蒸餾的純化作用提供4 1 %產率[2.7克] 之（甲基環戊二烯基）三甲基鉑。 實例7 甲基環戊二烯基鋰的製備 5 〇 〇毫升備有磁攪拌棒、熱電偶、和備有短路徑之12 公分冷凝器的夾套維格羅分餾柱之二頸圓底瓶中進料甲基 環戊二烯二聚物（2 00毫升）。將冷凝器安裝氮氣入口接 管和使用丙酮/C02浴冷卻到jo到-75 °C的收受燒瓶。使 燒瓶內容物進行溫和回流（1 4 5 - 1 7 0 °C )和收集且丟棄最 初約7 0毫升的餾出液。在微正氮氣壓下進實行蒸餾以將 周圍溼氣冷凝成餾出液減到最少。在5 0 · 5 3 °C下收集大部 -28- (26) 200406415 分甲基環戊二烯二聚物（約125毫升）°蒸餾重複兩次’ 再次丟棄前約25-30%以產生26克之甲基環戊二烯單體 [324.5毫莫耳，96.2% AUC，具有0.7%剩餘環戊二烯單 體]。冷卻之新鮮碎甲基環戊二烯中加人無水的無抑制劑 之THF ( 3 0 0毫升）和所得溶液短暫地抽氣且以氮氣沖洗 三次。經由均壓加入漏斗經3 0分鐘逐滴加入正-丁基鋰在 己烷中的溶液（2.5 Μ，118毫升，0.9當量），同時有效 率地攪拌反應混合物和以丙酮/C02浴冷卻燒瓶。除去冷 卻浴且使反應混合物溫熱至室溫過夜。如反應進展最初淡 黃色溶液變成黃色漿液。漿液壓力轉移至備有均壓加入漏 斗之1升乾三頸圓底瓶中，和以無水THF稀釋直到獲得 黃橘色的溶液（這需要加入290毫升的THF)。以二苯基 乙酸滴定所得甲基環戊二烯基鋰溶液指示其濃度爲 〇·38 Μ。 【圖式簡單說明】200406415 (1) 发明 Description of the invention Related applications This application is for US Provisional Application No. 60 / 388,054 on June 12, 2002 and US Provisional Application for June 12, 2002 6 0 / 3 8,998, the disclosures of which are incorporated herein by reference. [Technical field to which the invention belongs] The present invention relates to a liquid cyclopentadienyl trimethyl platinum compound, a method for preparing a thin film, coating or powder therefrom, and a method for preparing an organometallic compound. [Prior Art] Chemical vapor deposition is used to form a thin film of a substance on a substrate such as a wafer or other surface during the manufacture or processing of a semiconductor. In the chemical vapor deposition method, a chemical vapor deposition precursor (also known as a vapor deposition compound) is thermally, chemically, photochemically decomposed, or activated by a plasma to form a thin film having a desired composition. For example, a vapor-phase chemical vapor deposition precursor can be contacted with a substrate that is heated to a temperature above the decomposition temperature of the precursor 'to form a metal or metal oxide film on the substrate. Preferably, the chemical vapor deposition precursor is volatile, thermally decomposable and capable of producing a uniform film under the conditions of the chemical vapor deposition method. In the preparation of thin films by chemical vapor deposition, precursors which are liquid at room temperature are often preferred. The cyclopentadienyl trimethyl platinum compound is a very promising precursor of platinum (Pt) (2) (2) 200406415. Chemical vapor deposition is a technique for depositing a thin metal film on a surface. Although chemical vapor deposition precursors are usually preferably liquid, the two most available platinum species, the parent complex (cyclopentadienyl) trimethyl platinum (mp = 1 09 ° C) and (methyl cyclopentadiene) Alkenyl) trimethyl platinum (mp = 30 ° C) is all solid (Xue et al. J. AM. Chem. Soc 1 989, 3, 8 7 7 9). Liquid precursors are transported in most cases and produce more consistent evaporation (that is, solids can change the surface area, particle size, and crystallinity to produce uniform volatility). Liquid cyclopentadienyl trimethyl platinum complex (ethyl cyclopentadienyl) trimethyl platinum has been disclosed in U.S. Patent No. 5,929,267, in which it is used to form a platinum film. The compounds were characterized by 1 H NMR and CH analysis. Including melting ( < -7 8 ° C), density (· 1.5 g / cm 3), and viscosity (~ 5 cP). Trace metal analysis indicated impurities in the low ppm range. TG-DTA indicated about 0% non-volatile residue. Vapor pressure at 50-55 ° C was found to be ϋ 3 Torr. The compound is reported to be stable to air and water, and temperatures up to 150 ° C (although no half-life data are presented). However, the yield of this precursor from iodotrimethylplatin was moderately 51%. It also does not disclose the synthesis of organometallic platinum compounds on a large basis. Cyclopentadienyl trimethyl platinum complexes have been synthesized from Pt (IV) (e.g., K2PtCl6) and Pt (π) (e.g., K2ptCi4) sources. However, both paths are performed via the Pt (IV) trimethyl species of the general formula [XPt (CH3) 3] 4 (X = halide (eg I)) (see Figure 1, path A). This tetramer can be made more reactive by adding a halide displacement reagent such as a silver salt (e.g., ' silver trifluoromethanesulfonate). Tetrameric species of single ion pass -5- (3) (3) 200406415 are often achieved by extraction, precipitation, grinding and filtration. This tetramer compound can then be used to form many other compounds containing trimethylplatinum (including portions of these cyclopentadienyl molecules). No attempt has been revealed by synthesizing cyclopentadienyltrimethylplatinum complexes from K2PtCl6 or K2PtCl4 without a direct path to the isolated intermediates as discussed above. In the development method of forming a thin film by chemical evaporation deposition, there is still a continuing need for a chemical vapor deposition precursor which is preferably liquid at room temperature, has a high vapor pressure, and can form a uniform thin film. Therefore, there is a continuing need to develop novel compounds and explore their potential as precursors for chemical vapor deposition of thin film deposition. It is therefore desirable in the prior art to provide a chemical evaporative precursor, such as a liquid cyclopentadienyl trimethyl platinum precursor, in liquid form and which can be prepared in high yields. Also, it would be a significant advance in the art to provide a method for the scale-up preparation of organometallic platinum compounds with significant platinum recovery. Further, a one-step method for synthesizing organometallic platinum compounds is used in this technique, in which all operations are performed in a single container, and the compounds up to this group do not need to separate the intermediate complexes, which will be a significant progress. [Summary of the Invention] The invention states that part of the present invention relates to a liquid cyclopentadiene selected from (isopropylcyclopentadienyl) trimethylplatinum and (thirdbutylcyclopentadienyl) trimethylplatinum. Alkenyl trimethyl platinum compound. The invention also relates in part to a compound selected from (-6-(4) (4) 200406415 isopropylcyclopentadienyl) trimethyl platinum and (third butyl cyclopentadienyl) trimethyl by decomposition A method for preparing a film, coating, or powder from a cyclopentadienyl trimethyl platinum compound based on platinum, thereby producing a film, coating, or powder. A further part of the present invention relates to a method for preparing an organometallic compound, which comprises reacting a metal source compound, an alkylating agent, and a hydrocarbon or heteroatom-containing compound such as (cyclopentane) under reaction conditions sufficient to produce the organometallic compound. Dienyl compound). The invention has several advantages. For example, the method of the present invention can be used to produce organometallic compound precursors having different chemical structures and physical properties. This method can be used to prepare organometallic compounds, for example, cyclopentadienyltrimethylplatinum compounds. The method of the present invention can produce organometallic platinum compounds on a scale-up basis and has significant uranium recovery. This method is particularly suitable for scale-up preparation because it can be easily applied to the same equipment, some of the same reagents, and process parameters for making a wide range of products. This method is provided for the synthesis of an organometallic compound using a one-step method, in which all operations are performed in a single container, and compounds up to this point do not need to separate the intermediate complexes. Detailed description of the invention As shown above, the present invention relates in part to a method for preparing a film, coating or powder. The method includes decomposing at least one cyclopentadienyl trimethyl platinum compound selected from the group consisting of (isopropylcyclopentadimethyl) trimethyl platinum and (third butyl cyclopentadienyl) trimethyl platinum. A precursory step whereby a film, coating or powder is produced, as described further below. -7-(5) (5) 200406415 The present invention also relates in part to a 'one-pot, method' method for preparing organometallic compounds, which promotes both scaling up and platinum recovery. There is no loss of yield compared to previous techniques, and the present invention avoids labor-intensive and waste-producing material operations such as extraction. This method of the present invention also omits the formation and isolation of general intermediates, and reduces the amount of HC1 material (such as a 'chemical I agent' glassware) that is substantially required to include corrosion. In addition, because all transformations occur in one container until the final product is isolated (via sublimation / distillation), all other platinum compounds (eg, by-products) are confined to one location. Because platinum is an expensive metal, it is an economic advantage to recycle the reaction residue to recycle the remaining platinum, and ‘one pot, the method is more beneficial to this step. Product yields can range from about 60 to 99% or greater, preferably from about 75 to 99% or greater, and more preferably from about 80 to 99% or greater. The method of the invention provides unexpected advantages in many ways. Using a simplified one-pot synthesis process that promotes both scale-up and platinum recovery, the yield of materials from K2PtCU is 85-90%. The compound is a liquid, unlike (MMA-pentyl) dimethylplatinum and (methylcyclopentadienyl) trimethylplatinum. Considering that the yield of iodotrimethylplatinum from KdtCU is 65%, the direct comparison with the preparation of the above ethylcyclopentadienyl group will be adjusted to 85-90% to 43%. Enclosed in amphibians, such as pins, this doubling is a significant advantage. In addition, ethylcyclopentadiene is commercially available as a dimer with 97% purity, so cracking and fractionation are required to remove unsubstituted cyclopentadiene, followed by deprotonation. Similar isopropyl substituted ligands can be utilized with> 99% purity sodium salts. (Isopropylpentanyl) dimethyl pin is a kind of yellow liquid (-8- (6) 200406415 mp =-36 ° C, bp = 122 ° C at 5 Torr, d = rise above 2 4 ° C, viscosity = 2 · 7 c P at 30 ° C). The compound (that is, thermal stability) at 150 ° C is about 0.5 hours. When exposed to air, the color does slowly darken, so it needs to be down. The purity is measured by GC-MS (> 99.5%), HNMR (TGA (> 99.5%), and ICP-MS (> 99.9%). Platinum and (third butyl cyclopentadienyl) trimethyl platinum. This liquid platinum precursor can present advantages over the currently available cost advantages. These liquid platinum precursors can be determined by previous techniques. Prepared or prepared by the method of the present invention. Preferably, the platinum precursor is prepared by the one-pot method of the present invention, which produces the liquid platinum precursor compound under the reaction conditions of an alkylating agent and cyclopentane The reaction of dienyl compounds. As shown herein, the present invention includes a one-pot process for preparing organic gold, which comprises metal-derived compounds, alkylating agents, and hydrocarbons or heterogeneous examples (such as A cyclopentadienyl compound or a cyclopentadienyl-like compound. The method of the present invention enables scale-up preparation of organometals with significant platinum recovery. This method is particularly suitable for scale-up to be easily applied to a wide range of products Same reagents and recipes Parameters. This method provides a one-step method for the synthesis of organometallic compounds, which is carried out in all containers, and its compounds up to this point do not require a half-life of 1.43 g / millisecond if the compound is stored in nitrogen > 99%), the amount of pentadienyl) liquid platinum precursors and known conventional methods. The liquid state of the present invention includes a platinum compound that reacts with a reaction article sufficient to be a compound of a source compound, and is prepared in place. Due to the same equipment, a product using a one-step operation in a single intermixed product -9- (7) 200406415. The metal compound belongs to the source (among them); and gold should be mixed for the reaction of organic gold with no molar moles. RMgX is a larger and larger hydrocarbon, quasi-poly, and compound-derived compound for alkyl compounds, which can be selected from a wide variety of gold-containing compounds known in the art. Examples of metals include platinum, palladium and nickel. The platinum compound is preferably any metal compound, more preferably M2PtX6 M is metal, earth metal, silver or money, and X is halide, and K2PtCl6 is the best. The concentration of the source compound can vary over a wide range, and only the minimum amount of metal concentration required for the intended use and the minimum amount that will provide at least the amount of metal required for the genus compound of the present invention. Generally, the size of the compound However, the concentration of the metal-derived compound in the range of about 1 millimolar or less to about 0.0000 or more is sufficient for most parties. The chemical agent can be selected from a wide variety of materials known in the art. Examples of chemical compounds containing metal compounds include RAuLi (where R is a radical); (where R is a radical and X is a halide); and RLi (where R is a trimethyl platinum synthesized CH3). The concentration of the chemical may be It varies in a wide range, and only a minimal amount is required to provide the required concentration of the ibt group and the basis of the amount of alkyl group that will supply at least the organometallic of the present invention. In general, depending on the reaction mix, the concentration of the chemotherapeutic agent at about 1 millimolar or less to about 1000 millimolars or 箪 E should be sufficient for most methods. The solvent used in the method of the invention may be any saturated and unsaturated squar hydrocarbons, aromatic heterocyclics, haloalkanes, silylated hydrocarbons, ether ethers, thioethers, esters, lactones, hydrazones Amines, amines, polyamines-10- (8) (8) 200406415, nitriles, silicone oils, other aprotic solvents, or one or more of the above mixtures; more preferably hexanes, pentanes, Or dimethoxyethanes; and best ether or THF. Any suitable solvent can be used which will not unduly adversely interfere with the desired reaction. If desired, a mixture of one or more different solvents can be used. The amount of solvent used is not critical to the present invention and need only be an amount sufficient to dissolve the reaction ingredients in the reaction mixture. Generally, the amount of the solvent may range from about 5% by weight to about 99% by weight or more based on the total weight of the starting material of the reaction mixture. Reaction conditions such as temperature, pressure, and contact time can also vary widely and any suitable combination of these conditions can be used herein. The reaction temperature may be the reflux temperature of any one of the above solvents, and more preferably between about -100 ° C to about 25 ° C, and most preferably between about 0 ° C to about 25 ° C. Normal reactions are performed at room pressure and the contact time can vary from about seconds or minutes to hours or more. The reactants can be added to the reaction mixture or composition in any order. The reaction stopper can be selected from a wide variety of compounds known in the art. The reaction stoppers used in the present invention as examples include haloalkanes, ketones, alcohols, water, mineral acids, organic acids, carboxylic acids; and more preferably bromo-2-chloroethane, bromo- 2-fluoroethane, methane, and best;!, 2-dibromoethane. The concentration of the reaction stopper can be varied within a wide range, and only the minimum amount required for preparing the organometallic compound of the present invention is required. In general, depending on the size of the reaction mixture, a reaction stopper concentration in the range of about 1 millimolar or less to about 100 millimolars or more should be sufficient for most methods. -11-(9) (9) 200406415 The organometallic compound prepared by the method of the present invention can be represented by the formula lm (R) 3 'preferably LPt (R) 3, where l is a hydrocarbon or a heteroatom-containing group, which can be selected Carbohydrates, ginseng (pyrazolyl) borate, 3 kinds of pyridinium, dipyridines, tripyridines, 3 kinds of phosphines, diphosphines, triphosphines 3 kinds of fe: monoamines, monoamines , Triamine; more preferably P_diketonates' R is a linear or branched alkane or silane group, and μ is a metal selected from platinum, alumina and nickel. Preferably, L is selected from pentaapt0, non-, mono-, di-, tri-, tetra-, penta-substituted cyclopentadienyl, indenyl, cyclic and non-cycloallyl; R is methyl And M is platinum. More preferably, L is selected from cyclopentadienyl and cyclopentadienyl-like compounds. Examples of cyclopentadienyl-like molecular parts include cyclo-olefins, such as cyclohexadienyl, cycloheptadienyl, cyclooctadienyl rings, heterocyclics, aromatic rings, such as substituted or unsubstituted The concentration of benzyl (benzeny 1), and others, as known in the art. The concentration of hydrocarbons or heteroatom-containing compounds that provide L can be varied over a wide range 'and only need to provide the required L for use. The minimum amount that is the basis of the concentration and the amount of L that will provide at least the organometallic compound of the present invention. In general, depending on the size of the reaction mixture, an L concentration in the range of about 1 millimolar or less to about 100 millimolars or more should be sufficient for most methods. When a cyclopentyl compound is used in the reaction, cyclopentadienyl (or substituted analog) delivery can occur via a non-degraded diene (eg, cyclopentadiene), preferably cyclopentadiene Lithium, potassium, sharp, money, calcium, or magnesium salts of dienyl compounds. It can be added as a solid or as a solution with any of the solvents mentioned above, as a sodium salt of -12- (10) (10) 200406415, preferably -1 · 2 M solution. In the method of the present invention, the stirring time can be from about 0.1 to about 200 hours in all steps, and more preferably from about 2 to about 1000 hours for alkylation (for example, methylation) to stop the reaction. From about 2 to about 72 hours, and cyclopentadienyl added from about 0.1 to about 48 hours. More preferably, the stirring time may range from about 2 to 16 hours of methylation, 2 to 16 hours of stopping the reaction, and 0.1 to 1 hour of cyclopentadienyl addition. For the organometallic compound prepared by the method of the present invention, the purification effect can be via recrystallization, more preferably by extraction of the reaction residue (e.g., 'hexane) and chromatography, and most preferably by sublimation and distillation. Those skilled in the art will recognize that many variations can be made in the methods described in detail herein without departing from the scope or spirit of the invention as more specifically defined within the scope of the following patent applications. Examples of techniques that can be used to characterize the cyclopentadienyl trimethyl platinum compound formed by the above synthetic methods include, but are not limited to, analysis of hue, chromatography, nuclear magnetic resonance, thermogravimetric analysis, induced coupling Plasma mass spectrometry, vapor pressure and viscosity measurement. The relative evaporation pressure or relative volatility of the aforementioned cyclopentadienyl trimethyl platinum compound precursor can be measured by thermogravimetric analysis techniques known in the art. Equilibrium vapor pressure can also be measured, for example by evacuating all the gases from a closed container, and then introducing the compound's vapor into the container and measuring as known in the art. The cyclopentadienyl trimethyl platinum compound described herein first It is liquid at room temperature and is suitable for in-situ preparation of powders and coatings. For example, liquid cyclopentadiene -13- (11) 200406415 can be applied to a substrate, and then the temperature of the precursor can be used to form a metal layer on the substrate. The application of the liquid precursor to the substrate can be by paint or other techniques known in the art. Heating can be done by electrically heating the substrate in an oven, or by other coatings known in the art, by coating and decomposing the cyclopentadienyltrimethylplatinum with heat, thereby forming a first layer, followed by at least or Different other coatings are obtained, and obtained by heating. For example, the above-mentioned liquid cyclopentadienyl trimethyl platinum is atomized and sprayed on a substrate. Usable atomizing and spraying nozzles, sprayers and others are known in the art. In a preferred embodiment of the present invention, cyclopentadiene compounds, such as those described above, can be used in powder forming, thin deposition techniques. Compounds can be used with a single source of precursors and with more other precursors, for example, with other organometallic compounds or metal complexes, the method can also have more than one cyclopentadienyl precursor. , Such as above. Deposition can be performed in the presence of other gaseous components. In embodiments, the thin film deposition is performed on at least one non-reactive. Examples of non-reactive gases include inert gases, helium, and other gases that do not react with the cyclopentadienyl tertiary substance under process conditions. In other specific embodiments, it is performed in the presence of one less reactive gas. Some can be post-heated enough to spray or dip or oxidize metal oxides by using a heat gun. Layered precursors and the addition of a compound precursor that is the same as the precursor may also be used in the mist device method, such as the gas phase of an alkenyl trimethyl platinum film or coating, or may be used with one or heating at least one of its vapors. In the presence of a given trimethyl platinum compound in the presence of a specific carrier gas of the present invention, for example, nitrogen, hydrogen, methyl platinum compound, a thin film is deposited on the reactive gas before use.-14-(12) (12) 200406415 includes (But not limited to) hydrazine, oxygen, hydrogen, air, oxygen-enriched air, ozone (〇3), nitrogen oxide (N20), water vapor, organic vapor, and others. As is known in the art, the presence of an oxidizing gas, such as, for example, air, oxygen, oxygen-enriched air, 0 3, N 2 0, or a vapor of an oxidizing organic compound, facilitates the formation of a thin metal oxide film. The deposition methods described herein can be performed to form a thin film, powder, or coating including a single metal (e.g., a Pt-film), or a thin film, powder, or coating including a single metal oxide. It is also possible to deposit thin films, powders or coating mixtures' such as mixed metal oxide films. The mixed metal oxide film can be formed, for example, by using several organometallic precursors, at least one of which is selected from the cyclopentadienyl trimethyl platinum compound described above. Vapor-phase thin film deposition may be performed to form a thin film layer of a desired thickness, for example, in a range from about 1 nm to more than 1 mm. The precursors described herein are particularly useful for making films, for example, films having a thickness in the range of about 10 nm to about 100 nm. Thin films of platinum, for example, can be considered for making metal electrodes, especially P-channel metal electrodes for logic, and capacitor electrodes for DRAM applications. This method is also suitable for preparing a layered film in which the phases or components in at least two layers are different. Examples of the layered film include metal-insulator-semiconductor, and metal-insulator-metal. In a specific embodiment, the present invention relates to a method comprising the steps of thermally, chemically, photochemically or by plasma activation decomposing the aforementioned precursor vapor of a cyclopentadienylmethyl methyl platinum compound, whereby A thin film is formed on a substrate. For example, -15- (13) (13) 200406415 has a temperature sufficient to cause the cyclopentadienyl trimethyl platinum compound to decompose and form a thin film on the substrate by the vapor generated by a compound that is liquid at room temperature. Substrate contact. The cyclopentadienyl trimethyl platinum compound precursors can be used in chemical vapor deposition or, more particularly, metal organic chemical vapor deposition methods known in the art. For example, the above-mentioned cyclopentadienyl trimethyl platinum compound precursor can be used in atmospheric vapor pressure and low-pressure chemical vapor deposition methods. Compounds can be used in hot wall chemical vapor deposition, a method in which the entire reaction vessel is heated, and cold or warm wall type chemical vapor deposition, a technique in which only the substrate is heated. The above cyclopentadienyl trimethyl platinum compound precursor can also be used in a plasma or photo-assisted chemical vapor deposition method, in which the energy or electromagnetic energy from the plasma is used to activate the chemical vapor deposition precursor, respectively. . The compounds can also be used in ion-beam, electron-beam-assisted chemical vapor deposition methods, in which an ion beam or an electron beam is directed at a substrate, respectively, to supply energy for decomposing the precursors of chemical vapor deposition. Laser-assisted chemical vapor deposition can also be used, in which laser light is directed at a substrate to produce a photo-induced reaction of a chemical vapor deposition precursor. The method of the present invention can be performed in various chemical vapor deposition reactors, for example, Or cold-wall reactors, electric-assisted, beam-assisted or laser-assisted reactors, as known in the art. During chemical vapor deposition manufacturing, precursors that are liquid at room temperature are preferred and (isopropylcyclopentadienyl) trimethyl platinum and (third butyl cyclopentadienyl) trimethyl platinum Has properties that make them suitable as precursors for chemical vapor deposition. -16- (14) (14) 200406415 Examples of substrates that can be coated by the method of the present invention include solid substrates such as metal substrates such as A1, Ni, Ti, C0, Pt, Ta; metal $ 夕 化 (物 ', such as TiSi2, CoSi2, NiSi2; semiconductor materials, such as Si, SiGe, GaAs, IηP, diamond, GaN, SiC; insulators, such as si. 2, S i 3 N 4, H f Ο 2, T a 2 0 5, A12 O 3, barium hafnium titanate (b ST); barrier materials such as TiN., TaN; or on a substrate including a combination of materials In addition, 'films or coatings can be formed on glass, ceramic, plastic, thermosetting polymer materials, and on other coatings or film layers. In a preferred embodiment, film deposition is used in the manufacture of electronic components Or processed substrate. In other specific embodiments, the substrate is used to support a low-resistance conductor or light-transmitting film that is stable at high temperatures in the presence of an oxidant. The method of the invention can be performed to deposit a smooth A thin film with a flat surface. In one embodiment, the method is performed on a substrate for wafer manufacturing or processing. For example, the method is performed to form a film on a patterning substrate including features such as grooves, holes, or vias. In addition, the method of the present invention can also be used with other steps in wafer manufacturing or processing such as photomask, And other integrations. Chemical vapor deposition films can be deposited to a desired thickness. For example, the formed film can be less than 1 micron thick, preferably less than 500 nanometers and more preferably less than 200 nanometers. Also Films having a thickness of less than 50 nanometers can be prepared, for example, films having a thickness between about 20 and about 30 nanometers. The cyclopentadienyl trimethyl platinum compound precursors described above can also be used in the method of the present invention Thin films are formed by atomic layer deposition (ALD) or atomic layer nucleation (ALN) technology, during which the substrate is exposed to alternating pulses of precursors, oxidants, and inert -17- (15) (15) ¢ 00406415 Later layer deposition techniques are described, for example, in U.S. Patent Nos. 6,2 8 7,9 65 and U.S. Patent No. 6,3 42,27 7. The disclosures of both patents are incorporated herein by reference in their entirety. For example, 'in an ALD cycle' substrate Step-by-step exposure to: a) an inert gas; b) an inert gas of precursor vapors carried; c) an inert gas; and d) an oxidant, alone or in combination with an inert gas. In general, each step can be as short as the equipment allows (eg millimeters) and as long as the method requires (eg a few seconds or minutes). A cycle can be as short as milliseconds and as long as minutes. The cycle can repeat a cycle ranging from minutes to hours. The resulting film can be a few nanometers thin or thicker, for example, 1 millimeter (mm). The process of the invention can also be carried out using supercritical fluids. Examples of thin film deposition methods using supercritical fluids currently known in the art include chemical fluid deposition; supercritical fluid transport-chemical deposition; supercritical fluid chemical deposition; and supercritical immersion deposition. The chemical liquid deposition method, for example, is very suitable for preparing high-purity thin films and transforming complex surfaces and fillings with high appearance ratio. The chemical liquid deposition method is described in, for example, U.S. Patent No. 5,7 8 9,027. The use of supercritical liquids to form thin films is also disclosed in U.S. Patent No. 6,5 4 I 2 7 8 B 2. The disclosures of both patents are incorporated herein by reference in their entirety. In a specific embodiment of the invention, a heated patterning substrate is exposed to one or more precursors of a cyclopentadienyltrimethylplatinum compound in the presence of a solvent, such as a near-critical or supercritical liquid, such as, near-critical Critical or supercritical CO2, the solvent liquid is provided at a pressure above about 1,000 psig and at a temperature of at least about 30 ° C. -18- (16) (16) 200406415 The precursor is decomposed to form a metal thin film on the substrate. The reaction also produces organic materials from the precursor. The organic material is dissolved and easily removed from the substrate by a solvent solution. For example, a metal oxide thin film can be formed by using an oxide. In ~ embodiments, the deposition process is performed in a reaction chamber covering one or more substrates. The substrate is heated to the desired temperature by heating the entire chamber, e.g., via a furnace. Vapor of a cyclopentyl-dimethylplatinum compound can be generated, for example, by applying a vacuum to the chamber. For low-boiling compounds, the chamber is hot enough to cause the compounds to evaporate. When the vapor comes into contact with the surface of the heated substrate, it decomposes and forms a metal or metal oxide film. As mentioned above, the precursors of the cyclopentyl dimethyl compound may be used alone or in combination with one or more components, for example, other organometallic precursors, inert carrier gases, or reactive gases. In a system that can be used to prepare a thin film by the method of the present invention, the feedstock can be directly connected to a gas-blend manifold to produce a process gas that is supplied to a deposition reactor where thin film growth is performed. Raw materials include, but are not limited to, carrier gases, reactive gases, flushing gases, precursors, etching / cleaning gases, and others. The precise control of the method gas composition is accomplished using mass flow controllers, valves, pressure transducers, and other devices, as known in the art. The exhaust manifold delivers the gas leaving the depositor and bypasses to the vacuum pump. Mitigation system ’The vacuum pump is downstream and can be used to remove any hazardous substances from the exhaust. The deposition system can be equipped with an in-situ analysis system, including a residual gas analyzer, which allows the measurement of the method gas composition. Control and data acquisition systems can monitor various method parameters (eg, temperature, pressure, flow rate, etc.). The above-mentioned cyclopentadienyl trimethyl platinum compound precursor can be used to prepare a thin film including (17) (17) 200406415 a single metal, for example, a Pt-film, or a thin film including a single metal oxide. Mixed films can also be deposited, such as mixed metal oxide films. These films are prepared, for example, by using several organometallic precursors, at least one of which is selected from the cyclopentadienyl trimethyl platinum compound described above. For example, 'a metal film can also be formed by using no carrier gas, vapor, or other oxygen source. Films formed by the methods described herein can be made by techniques known in the art, such as by X-ray diffraction, Augar spectroscopy, X-ray photoelectron emission spectroscopy, atomic forced microscopy, scanning electron microscopy, Other techniques known in the art. The electrical stability and thermal stability of the film can also be measured by methods known in the art. Various modifications and changes of the present invention will be obvious to those skilled in the art, and it should be understood that such modifications and changes will be included in the scope of the present application and the spirit and scope of the scope of patent application. [Embodiment] Example 1 The reaction described in FIG. 1 was completed as reported by Boardma η and Nemark (Nuclear Magnetic Resonance in Chemistry 1 929, 2 0, 4 8 1), Path A to synthesize other rings Pentadienyl platinum compound. In this case, isopropylcyclopentane sodium was used to generate a novel compound that was not previously synthesized. The yield of the iodotrimethylplatinum synthesis was 80% (reported as 89%). Later (isopropylcyclopentadiyl) trimethyl platinum (a yellow liquid) yielded 88%. The overall yield (two steps) was 70%. Miscellaneous -20- (18) (18) 200406415 Example 2 The reaction described in Figure 1 is completed, path B. All glassware was dried overnight. A 2-liter three-necked round-bottomed bottle equipped with a stir bar, an addition funnel fitted with a baffle, a vacuum connection to the Schlenk line, and a baffle. After drying under nitrogen, the flask separator was briefly removed to add K2PtCl6 (41.5 g, 85. 5 mmol). The system was flushed again with nitrogen. Anhydrous, inhibitor-free tetrahydrofuran (THF) (850 ml) was transferred to an addition funnel and added to the flask. Start stirring and cool the yellow slurry to 0 °. A 1.4 M solution of methyl lithium in ether (500 ml, 700 mmol) was transferred to the addition funnel. The methyllithium solution was added dropwise (over 5-6 hours) at a rate such that the temperature of the reaction mixture was always fixed below 5 ° C. A slower addition rate is required at the beginning of the addition, after 2 hours only 20% of the total volume is added. Once the methyllithium addition was complete, the reaction mixture was allowed to warm to room temperature. If stirring is continued overnight (~ 16 hours), the yellow-brown suspension fades to pale yellow-brown. The suspension was cooled to 0 ° C again. Add 1,2-dibromoethane (40 ml, 460 mmol) in a nitrogen purge so that the temperature of the reaction mixture is always fixed below 5 ° C and added dropwise (over 2-3 hours). A slower rate of addition was required at the beginning of the addition, and only 20% of the total volume was added after 2 hours. The reaction mixture was stirred at 0 ° C for ~ 4 hours, then allowed to warm to room temperature while stirring overnight (~ 16 hours). The solvent and excess 1,2-dibromoethane were removed under reduced pressure (~ 0 · 1 Torr) and mild heat (30-40 ° C). The solid was left under vacuum for 3 hours. The brown residue was suspended in THF, and a solution of sodium isopropylcyclopentadiene (12.2 g-21-(19) (19) 200406415, 94 mmol) in 0.6 M THF (via 20-30 minutes). After stirring for 1 hour, the solvent was removed under reduced pressure, and the isolated product was evaporated through a 'short path' to produce a yellow liquid 'body with a yield of 87%. Example 3 Complete the reaction described in Figure 1, Path B. All glassware was dried overnight. A three-necked round-bottomed bottle equipped with a stir bar is equipped with a septum, a capped addition drain 4, a vacuum connection to the Schlenk line, and a septum. After drying under nitrogen, the flask separator was briefly removed to add K2PtCl6 (41.5 g, 85.5 mmol). The system was flushed again with nitrogen. Anhydrous, inhibitor-free tetrahydrofuran (THF) (85 ml) was transferred to the addition funnel and added to the flask. Agitation was started and the yellow slurry was cooled to 0 fcC. A 1.4 M solution of methyllithium in ether (50 ml, 70 mmol) was transferred to the addition funnel. The methyllithium solution was added dropwise (over 3-4 hours) at a rate such that the temperature of the reaction mixture was always fixed below 5 ° C. A slower rate of addition is required at the beginning of the addition, after 1 hour only 20% of the total volume is added. Once the methyllithium addition was complete, the reaction mixture was allowed to warm to room temperature. If the stirring is continued for 3-4 hours, the yellow suspension will fade to colorless. The reaction was allowed to stir overnight (~ 16 hours). The suspension was cooled down again. Nitrogen was flushed with 1,2-dibromoethane (40 ml, 460 mmol) so that the temperature of the reaction mixture was fixed at 5 at all times. (: The following rates are added dropwise (over 1 hour). A slower addition rate is required at the beginning of the addition, after 20 minutes only 20% of the total volume is added. The reaction mixture is stirred at 0 ° C for ~ 4 hours 'Then let warm to room temperature while stirring overnight (~ 16 hours). Remove the solvent and excess under reduced pressure (~ 0 · 1 Torr) and mild heat (~ 30 ° C) ι, 2-dibromoethane. To help completely remove 1,2 · dibromoethane, little THF was added to the solid residue and re-evaporated. The solid was left under vacuum for 3 hours. The brown residue was suspended in 1. 3M THF solution of sodium methylcyclopentadiene (prepared from double-distilled methylcyclopentadiene and NaH) (1.0 g, 10 mmol) in THF (after 20-30 Minutes). After stirring for 1 hour, the solvent was removed under reduced pressure (~ 0.5 Torr), and distillation or sublimation was performed via a 'short path' (reported sublimation temperature: 23 t, at 0.0 5 3 mm). White crystals were produced in a yield of 65-75%. Purity: > 99.5% by GC / MS, > 99% by NMR. < 0.1% NVR via TGA. Example 4 Preparation of (methylcyclopentadienyl) trimethylplatinum using methyllithium and 20 volumes of THF in an alkylation step. A magnetic stir bar, thermocouple, two pressure equalization funnels and connection to A 500 ml roasted, dry, four-necked round bottom flask of nitrogen / vacuum line of the gas bubbler was charged with potassium hexachloroplatinate (10 g, 20 · 58 mmol). The system was closed and briefly evacuated, then flushed with nitrogen. Repeat two rinse cycles. The pressure of anhydrous THF (200 mL, 20 vol.), Anhydrous, without inhibitor was transferred to the addition funnel using slightly positive nitrogen pressure (3-5 psi), and then discharged into the flask. The resulting yellow slurry was cooled to 0 ° C using an ice / ethanol bath and then flushed twice with nitrogen. Using slightly positive nitrogen pressure (3-5 psi), transfer the pressure of a solution of methyl lithium in acetic acid (105.5 ml, 168.8 mmol, 8.2 equivalents) to -23- (21) (21) ¢ 00406415 into the funnel, then Add in 2-5 ml portions and 5 min intervals over 6 hours while the temperature of the reaction mixture is maintained between ~ 2 ° C and 4 ° C. The initial yellowish slurry turned yellow / yellow-brown in 1 hour. The 'yellowish-brown tone' faded when methyl lithium was added each time, but regenerated as the reaction proceeded. At the end of the methyllithium addition, the appearance of the batch was a pale yellow / yellow brown and cloudy solution. The reaction mixture was allowed to slowly warm to room temperature overnight. After further stirring for 14 hours, the appearance of the batch was an off-white cloudy solution. The reaction mixture was cooled to 0 C and 1,2 · dibromoethane (10 ml, 5.2 equivalents) was flushed with nitrogen by slowly adding nitrogen through an addition funnel to stop the reaction. A lot of gas evolution was initially observed after stopping, but this evolution stopped after about 4 ml of dibromoethane was added. The reaction mixture was allowed to warm to room temperature and further stirred for 18 hours to provide a yellow-brown turbid solution. The flask was fixed in a heating mantle, a short path distillation head was installed, and most of the solvent was distilled at 35 ° C under a medium vacuum (about 140 mm Hg). Remove the remaining 1,2-dibromoethane at 1.5 torr and 3 5-40 ° C over 3 hours. Anhydrous, inhibitor-free THF (80 ml, 8 volumes) was added to the flask and the resulting suspension was stirred vigorously to provide a fine solid brown suspension. A solution of MeCpLi in THF / hexane [60 mL, 0.3 8 M, 1.1 equivalents] was slowly added to the suspension over 30 minutes and the resulting mixture was stirred at room temperature for 1 hour. The brown slurry pressure was transferred into a 500 ml dry round bottom flask and the solvent was stripped on a rotary evaporator under reduced pressure at 2 8 C to produce a brown flowing hair solution. Anhydrous heptane (200 ml ' 20 volume) was added to the slurry and the suspension was stirred vigorously. Due to the addition of Gengyuan 'a large amount of solids stuck to the flask. Stop stirring and allow the solids to settle. The pressure of the supernatant liquid was transferred into a 500 ml flask and concentrated on a rotary evaporator at 2 8 -3 5 ° C to yield -24- (22) (22) 200406415 yellow-brown oily residue [7 · 95 g] . The product was purified by vacuum distillation (0.13 Torr, bp 4 6-4 7 ° C) to provide 68.5% yield [4.5 g] of the title complex. Analysis by GC indicated that 92.5% (AUC wide purity and 0.9% (AUC) (methylcyclopentadienyl) trimethyl platinum and 5.8% (AUC) dodecane pollutants came from The n-hexyl lithium of MeCpLi was prepared from MeCp monomers. The 1H NMR spectrum was consistent with the specified structure. Example 5 (methylcyclopentadienyl) trimethyl was used in the alkylation step with methyllithium and 10 volumes of THF Preparation of base platinum 5000 ml of a dry three-necked round-bottomed flask equipped with a magnetic stir bar, thermocouple, pressure equalization funnel, and nitrogen / vacuum line connected to a gas bubbler was charged with potassium hexachloroplatinate (1 〇 G, 2 0.5 8 millimoles). The system was closed and briefly evacuated, and then flushed with nitrogen. Repeat the two flush cycles. Use micro-positive nitrogen pressure (3-5 p si) to dry anhydrous, inhibitor-free THF ( (100 ml, 10 vol.) The pressure was transferred to the addition funnel, and then discharged into the flask. The resulting yellow slurry was cooled to 0 ° C with a coolant, and then flushed twice with nitrogen. Use slightly positive nitrogen pressure (3-5 psi) A solution of methyl lithium in diethyl ether (105.5 ml, 168.8 mmol, 8.2 equivalents) was transferred to an addition funnel, and then It was then added to 2-5 ml portions over 6 hours while the temperature and temperature of the reaction mixture was maintained between 0-2 ° C. The cooler was turned off and the reaction mixture was slowly warmed to room temperature and stirred overnight. The reaction mixture Cooled to 0t: and 2-dibromoethane (10 ml '5 · 2 equivalents) was stopped by slowly adding nitrogen through an addition funnel over 2 h. The reaction mixture was allowed to warm to room temperature and- 25-(23) (23) 200406415 Further stirring overnight to produce a yellow-brown turbid solution. The flask was fitted with a short path distillation head, the coolant liquid was set at 40 ° C, and under a medium vacuum (about 140 mm Hg). Most solvents were distilled at 3 5 ° C. The remaining 1,2-dibromoethane was at 1.0 Torr and 40. (: Further removed in 2 hours. Anhydrous and inhibitor-free TB F (1 (0 ml, 10 vol) was added to the brown solid residue and the resulting suspension was stirred vigorously to produce a fine solid brown suspension. An aliquot from the slurry indicated by GC analysis that a small amount of dibromoethane was still present In the residue. The solvent was further distilled as described above and the residue was suspended in T HF (80 mL, 8 volumes) and stirred to produce a brownish brown slurry. Further GC analysis indicated that only traces of dibromoethane were present in the residue. MeCpLi solution in THF / hexane [63 mL, 0.36M , 1.1 equivalent] was slowly added to the suspension over 30 minutes and the resulting mixture was stirred at room temperature for 1 hour. Most of the THF (140 mm Hg, 35 ° C. was distilled under reduced pressure, about 60 ml of THF was removed ). Anhydroheptane (200 ml, 20 volumes) was added to the resulting brown slurry, and the suspension was stirred vigorously for 1 hour to extract the product. The stirring was stopped, the solids were allowed to settle, and the supernatant pressure was transferred to a 500 ml flask. Anhydrous THF (40 ml) and anhydrous heptane (160 ml) were added to the solid residue, and the suspension was stirred vigorously for 1 hour to further extract the product. Combine the above solution with the original extract and remove the solvent under reduced pressure on a rotary evaporator to produce a yellow-brown slurry. Anhydrous THF (50 ml) was added to the slurry, and the resulting brown solution was transferred to a 100 ml flask and the solvent was further removed under reduced pressure to give a brown oil [1 2 · 59g]. The product was distilled by vacuum ( 0.3 to 0.4 Torr, bp 56-5 7 ° C] Purified to give the title complex in 61% yield [4.0 1 g]. The initially isolated colorless oil solidified at room temperature (24) 200406415 upon standing Analysis to yield an off-white solid (mp = 29-3 0 ° C GC indicated purity > 99% (AUC) and < 0.1% (methylcyclopentadienyl) trimethyl platinum. 1Η N MR spectrum is consistent with the finger. All trace metals indicated by further trace metal analysis by ICPMS, therefore > 99.999% Pt content. Example 6 Preparation of (methylcyclo) trimethylplatinum using methylmagnesium chloride in an alkylation step 500 ml equipped with a magnetic stir bar, thermocouple, pressure equalization, nitrogen added to a gas bubbler / Vacuum line of dry three-neck round bottom bottle of potassium chloroplatinate (10 g, 20 · 58 mmol). The system was closed with gas' and then flushed with nitrogen. Repeat two rinse cycles. Use (3 »5 psi) to transfer the pressure of anhydrous THF (100 ml) without inhibitor to the addition funnel, then drain into the flask. The resulting yellow slurry was allowed to cool to 0 ° C with an alcohol bath, and then methylmagnesium chloride in TBF (56.3 ml, 3.0 M,) 68 · 8 mmol was flushed with nitrogen using slightly positive nitrogen pressure (3-5 psi). Moore, 8.2 equivalents) to the addition funnel 'and then added to the slurry dropwise over the course of one hour. The contents were slowly warmed to room temperature and stirred overnight. The reaction mixture was cooled and the reaction was stopped by slowly adding nitrogen in a single portion, i.e. 2-20 ml (5 2 equivalents). The reaction mixture was allowed to stir gently for a further 2.5 days. The flask was fitted with a short path distillation head and steamed at 35 ° C under moderate vacuum (about 40 mm Hg). With the structure of AUC) (3.57 ppm pentadienyl funnel and Lianzhong feed six and briefly pumped with a slight positive nitrogen pressure, 10 volumes were washed twice with ice / ethyl. The solution in the pressure transfer reaction was mixed to 0 ° c Ethyl bromide (warm to room temperature and heating mantle to distill most of the solvent from 27- (25) (25) 200406415. Residual ι, 2-dibromoethane is further removed at 1.0 Torr and 40 ° C over 2 hours Anhydrous, inhibitor-free THF (80 ml, 8 volumes) was added to the off-white solid 'residue and the suspension was stirred vigorously at room temperature for 4 hours. A solution of MeCpLi in THF / hexane [60 ml, 0 · 38 M, 1.1 equivalent] was slowly added to the slurry over 30 minutes and the resulting mixture was vigorously disturbed for 4 hours at room temperature. The resulting liquid was transferred to a 500 ml flask and the THF was removed on a rotary evaporator to A yellow-brown solid residue was produced. Anhydrous heptane (200 ml) was added to the residue but no dissolution was achieved. Anhydrous TBF (200 ml) was added, a flask equipped with a Claisen tube and a mechanical stirrer, and The suspension was stirred at room temperature overnight. The supernatant was transferred to a 500 ml flask and then Stripping on a rotary evaporator using a 100 ml flask to produce a yellow-brown oily residue [1 2.8 7 g]. Purification by distillation from 0.2 5 to 0.5 0 Torr (bp 5 5 ° C) provides 4 (Methylcyclopentadienyl) trimethylplatin in a 1% yield [2.7 g] Example 7 Preparation of methylcyclopentadienyl lithium 500 ml was equipped with a magnetic stir bar, thermocouple, and Methylcyclopentadiene dimer (200 ml) was fed into a two-necked round bottom flask of a jacketed Vigro fractionating column with a short path of 12 cm condenser. A nitrogen inlet was installed on the condenser and acetone was used. The / C02 bath cooled the receiving flask to jo to -75 ° C. The flask contents were gently refluxed (145-170 ° C) and the initial approximately 70 ml of distillate was collected and discarded. Distillation was performed under nitrogen pressure to minimize the condensation of surrounding moisture into distillate. Collect most of the -28- (26) 200406415 methylcyclopentadiene dimer ( (Approximately 125 ml) ° Distillation is repeated twice 'before discarding about 25-30% again to produce 26 g of methylcyclopentadiene monomer [324.5 mmol, 96.2% AUC, with 0.7% residual Cocyclopentadiene monomer]. Cool fresh ground methyl cyclopentadiene was added with anhydrous THF (300 ml) without inhibitor and the resulting solution was briefly evacuated and flushed with nitrogen three times. The pressure funnel was added dropwise a solution of n-butyllithium in hexane (2.5 M, 118 mL, 0.9 eq.) Over 30 minutes while efficiently stirring the reaction mixture and cooling the flask with an acetone / CO 2 bath. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature overnight. As the reaction progressed, the light yellow solution turned into a yellow slurry. The pressure of the slurry was transferred to a 1 liter dry three-necked round bottom flask equipped with a pressure equalization funnel, and diluted with anhydrous THF until a yellow-orange solution was obtained (this required the addition of 290 ml of THF). The titration of the obtained methylcyclopentadienyl lithium solution with diphenylacetic acid indicated that its concentration was 0.38M. [Schematic description]
圖1描述一種製備環戊二烯基三甲基鉑化合物之新合 成路徑（Β )及一種用以製備環戊二烯基三甲基鉑化合物 之先前技藝合成路徑（A )。 •29-Figure 1 depicts a new synthetic route (B) for preparing a cyclopentadienyl trimethyl platinum compound and a prior art synthetic route (A) for preparing a cyclopentadienyl trimethyl platinum compound. • 29-