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題名 | Rotational Behavior of Diethyldithio-phosphate Molybdenum Complexes: [Mo(MeCN)(η[fec4]-C[feb0]H忦)(CO)[feaf]{η[feb4]-S[feaf]P(OEt)[feaf]}]=二乙氧基硫代磷酸根配位基鉬金屬錯化物[Mo(MeCN)(η[fec4]-C[feb0]H忦)(CO)[feaf]{η[feb4]-S[feaf]P(OEt)[feaf]}]在溶液中的旋轉行為 |
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作者 | 易光輝; 林英智; | 書刊名 | 弘光學報 |
卷期 | 33 1999.04[民88.04] |
頁次 | 頁169-180 |
分類號 | 345.2 |
關鍵詞 | 鉬金屬; 二乙氧基硫代磷酸根配位基; 三角旋轉機構; Molybdenum; Diethyldithiophosphate; Trigonal twist; |
語文 | 英文(English) |
中文摘要 | 將化合物M(CO)��(pip)��(pip=piperdine)(M=Mo,W)與NH�淞�烈(OEt)�祟韝A睛溶 劑中迴流,Et �� NBr 的存在下,可得到乙氧基硫代磷酸根配位的錯合物 [Et �� N][M(CO) �� { η�� -S �� P(OEt) �� }](1,M=Mo;2,M=W)。化合物 1 於乙睛溶劑中與 1- 溴丙烯作 用, 可得到氧化加成的產物 [MO(MeCN)( η�� C �� H �N (CO) �� { η�� -S �� P(OEt) �� }](3)。化合物 3 在溶液中的旋轉機構可經由變溫氫核磁共振光譜儀 (�� HNMR) 加以偵 測。得知其旋轉機構是:乙睛及硫代磷酸根的兩個硫原子所形成的三角面與丙烯墓及兩個碳 基所形成的三角面相對旋轉 (trigonal twist)。 |
英文摘要 | The air-sensitive diethyidithiophosphate complex [Et�淇][M(CO)�現η��- S �� P(OEt) �� }] (1, M = Mo; 2, M = W) are accessible by the reaction of M(CO) �� (pip) �� (pip = piperidine) (M = Mo, W) with NH �� S �� P( OEt) �� in refluxing acetonitrile in the presence of Et �� NBr. Complex 1 reacts with allyl bromide in CH�蚓N to give the oxidative addition complex [Mo(MeCN)( η�� -C �� H �N )(CO) �� { η�� -S �� P(OEt) �� }] (3). The rotational behavior of complex 3 in solution was detected by variable-temperature �� H NMR spectroscopy. The mechanism can be described as a trigonal twist, in which the rotation of the triangular face formed by the MeCN and the two sulfur atoms relative to the face formed by the allyl and the two carbonyl groups. |
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