Cluster Condensation by Thermolysis: Synthesis of a Rhomb-Linked Re12Se16 Dicluster and Factors Relevant to the Formation of the Re24Se32 Tetracluster
Cluster Condensation by Thermolysis: Synthesis of a Rhomb-Linked Re12Se16 Dicluster and Factors Relevant to the Formation of the Re24Se32 Tetracluster
复制标题
热解团簇缩合：菱形连接的 Re12Se16 二团簇的合成以及与 Re24Se32 四团簇形成相关的因素
DOI：
10.1021/ic970727x
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发表时间：
1997
影响因子：
4.6
通讯作者：
R. H. Holm
中科院分区：
文献类型：
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作者：
Zhiping Zheng;R. H. Holm
在 AgSbF6 存在下，簇 cis-[Re6Se8(PEt3)4I2] 与中性配体 L 进行取代反应，得到顺式二取代簇 [Re6Se8(PEt3)4L2]2+ (L = MeCN (6)、t-BuCN、DMF、Me2SO (9)）。簇 6 与吡啶反应生成 [Re6Se8(PEt3)4(py)2]2+。 31P NMR 谱和 [9](SbF6)2 的晶体结构证明了立体化学的保留，这表明两个 Me2SO 配体在面封端八面体 [Re6(μ3-Se)8]2+ 核的相邻 Re 位点处形成 O 键合。 cis-[Re6Se8(PEt3)4L2]2+ 簇作为热解条件下寡聚簇的可能前体而受到关注，其中一个或两个配体 L 被去除。橙红色 [6](SbF6)2 (180 °C，24 h) 热解得到棕绿色结晶产物，经 X 射线结构测定鉴定，含有双簇 [Re12Se16(PEt3)8(MeCN)2]4+ (11)。两个 [Re6Se8]2+ 团簇单元通过 Re2Se2 菱形桥接以提供中心对称核心 [Re12(μ3-Se)14(μ4-Se)2]4+，建立了最新的...
The cluster cis-[Re6Se8(PEt3)4I2] undergoes substitution reactions with neutral ligands L in the presence of AgSbF6 to afford the cis-disubstituted clusters [Re6Se8(PEt3)4L2]2+ (L = MeCN (6), t-BuCN, DMF, Me2SO (9)). Cluster 6 reacts with pyridine to give [Re6Se8(PEt3)4(py)2]2+. Retention of stereochemistry was demonstrated from 31P NMR spectra and the crystal structure of [9](SbF6)2, which revealed the two Me2SO ligands to be O-bonded at adjacent Re sites of the face-capped octahedral [Re6(μ3-Se)8]2+ core. The clusters cis-[Re6Se8(PEt3)4L2]2+ are of interest as possible precursors to oligomeric clusters under thermolysis conditions where one or both ligands L are removed. Thermolysis of orange-red [6](SbF6)2 (180 °C, 24 h) afforded a brown-green crystalline product identified by an X-ray structure determination to contain the dicluster [Re12Se16(PEt3)8(MeCN)2]4+ (11). Two [Re6Se8]2+ cluster units are bridged by a Re2Se2 rhomb to afford the centrosymmetric core [Re12(μ3-Se)14(μ4-Se)2]4+, established recen...