Synthesis, Fluxional Behavior and Crystal Structure of Ethoxyldithiocarbonate Molybdenum Complex: [Mo(CH_3CN)(η^ 3-C_3H_5)(CO)_2(η^2-S_2COEt)]

乙氧基二硫代碳酸鉬金屬錯化合物的合成、溶液中的流變行為與晶體構造[Mo(CH_3CN)(η^ 3-C_3H_5)(CO)_2(η^2-S_2COEt)]

易光輝(Kuang-Hway Yih) ； 李錦祥(Gene-Hsiang Lee) ； 黃守齡(Shou-Ling Huang) ； 王瑜(Yu Wang)

《弘光學報》 40期 (2002/11) Pp. 1-5

https://doi.org/10.6615/HAR.200211.40.01

摘要

將化合物[Mo(CH_3CN)(η^ 3-C_3H_5)(CO)_2Br]與KS_2COEt於氰甲烷溶劑中反應，可得到第一個18電子空氣敏感的乙氧基二硫代碳酸鉬金屬的錯合物[Mo(CH_3CN)(η^ 3-C_3H_5)(CO)_2(η^2-S_2COEt)]（1）。化合物1經由X光繞射儀解析出單晶結構數據為：空間群為：P2_1/c a = 7.2178(1) Å b = 12.2401(2) Å c = 16.1978(3) Å ，β= 100.394(1)O V = 1407.54(4) Å3 Z = 4 R = 0.017 Rw = 0.044。化合物1在溶液中的旋轉機構可經由溫氫核磁共振光譜儀(^1H NMR)加以偵測。得知其旋轉機構是：氰甲烷及乙氧基二硫代碳酸根的兩個硫原子所形成的三角面與丙烯基及兩個羰基所形成的三角面相對旋轉（trigonal twist）。

關鍵字

乙氧基二硫代碳酸根配位基 ； 溶液中的流變行為 ； 鉬金屬

並列摘要

The first 18-electron air-sensitive ethoxyldithiocarbonate molybdenum complex [Mo(CH_3CN)( η^3- C_3H_5)(CO)2(η^2-S_2COEt)] (1) is accessible by the reaction of [Mo(CH_3CN)( η^3-C_3H_5)(CO)_2Br] with KS_2COEt in acetonitrile. The single crystal structure of complex 1 has been determined by X-ray diffraction analysis. Crystal data for 1: space group, P21/c with a = 7.2178(1) Å, b = 12.2401(2) Å, c = 16.1978(3) Å, β= 100.394(1)o, V = 1407.54(4) Å3, Z = 4. The structure was refined to R = 0.017 and Rw = 0.044. The rotational behaviors of complex 1 in solution state were detected by variable-temperature 1H NMR spectroscopy. The mechanism of rotation can be described as a trigonal twist, in which the rotation of the triangular face formed by the nitrogen ligand and the two sulfur atoms relative to the face formed by the allyl and the two carbonyl groups.

並列關鍵字

ethoxyldithiocarbonato ligand ； rotational behavior ； molybdenum

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