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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvent and Structural Effects on Ultrafast Chelation Dynamics of Arene Chromium Tricarbonyl Sulfide Derivatives
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Solvent and Structural Effects on Ultrafast Chelation Dynamics of Arene Chromium Tricarbonyl Sulfide Derivatives

机译：芳烃三羰基铬硫化物衍生物的超快螯合动力学的溶剂和结构效应

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摘要

The chelation dynamics of three new [Cr{6-C6H5C(O)R}(CO)3] complexes, 1 [R = CH2(SCH3)], 2 [R = CH(SCH3)2], and 3 [R = C(SCH3)3], has been investigated on the picosecond to millisecond time scales by UV pump/IR probe transient absorption spectroscopy following photodissociation of CO in room temperature n-heptane, tetrahydrofuran (THF), and acetonitrile. In n-heptane, UV irradiation of 1, 2, or 3 dissociates CO to initially yield a Cr-S chelate (in which the pendant sulfide moiety is coordinated to the metal center) and a transient Cr-heptane solvate in approximately 1:2, 1:2, and 2:1 ratios, respectively. The Cr-heptane solvate is unstable and converts to the Cr-S chelate within 30 ns in each case. Irradiation of 2 or 3 in THF yields both the Cr-S chelate and Cr-THF solvate in approximately 1:3 and 1:1 ratios, respectively. The Cr-THF solvate converts to the Cr-S chelate on the second or longer time scale. All three complexes appear to yield the Cr-NCCH3 solvate exclusively within 50 ps following irradiation in acetonitrile. The solvent effect on chelation is in striking contrast to that previously reported for the analogous RCpMn(CO)3 derivatives, 4-6. In acetonitrile, only chelation is observed for the Mn series and only solvent coordination is observed for the Cr series, but in heptane both chelation and solvent coordination are observed in both series.
机译：三种新的[Cr {6-C6H5C（O）R}（CO）3]配合物的螯合动力学，其中1 [R = CH2（SCH3）]，2 [R = CH（SCH3）2]和3 [R = C（SCH3）3]，是在室温正庚烷，四氢呋喃（THF）和乙腈中CO光解离后，通过紫外泵/ IR探针瞬态吸收光谱法在皮秒至毫秒级的时间内进行研究的。在正庚烷中，用1、2或3的UV照射使CO解离，最初生成Cr-S螯合物（其中的侧链硫化物部分与金属中心配位）和大约1：2的瞬态Cr-庚烷溶剂化物，1：2和2：1的比例。 Cr-庚烷溶剂化物是不稳定的，在每种情况下均会在30 ns内转化为Cr-S螯合物。在THF中照射2或3时，分别以约1：3和1：1的比例生成Cr-S螯合物和Cr-THF溶剂化物。 Cr-THF溶剂化物在第二或更长时间段内转化为Cr-S螯合物。在乙腈中照射后，所有三种络合物似乎仅在50 ps内产生Cr-NCCH3溶剂化物。溶剂对螯合的影响与先前报道的类似RCpMn（CO）3衍生物4-6形成鲜明对比。在乙腈中，仅观察到Mn系列的螯合，而仅观察到Cr系列的溶剂配位，但是在庚烷中，两个系列均观察到螯合和溶剂配位。

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