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通过[PhTE]阴离子（T = Si，Sn；E = S，Se）对三元有机四价金属-铜硫族化物簇进行系统合成

Systematic Access of Ternary Organotetrel-Copper Chalcogenide Clusters by [PhTE ] Anions (T=Si, Sn; E=S, Se).

作者信息

Rinn Niklas, Guggolz Lukas, Hou Han Yu, Dehnen Stefanie

机构信息

Fachbereich Chemie, Philipps Universität Marburg, Hans-Meerwein Straße 4, 35037, Marburg, Germany.

出版信息

Chemistry. 2021 Aug 2;27(43):11167-11174. doi: 10.1002/chem.202101139. Epub 2021 Jun 22.

DOI:10.1002/chem.202101139
PMID:33871889
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8453927/
Abstract

Fragmentation reactions of organotetrel chalcogenide heteroadamantane-type clusters [(PhT) E ] (T/E=Si/S (1); Si/Se; Sn/S, and Sn/Se) by addition of the corresponding sodium chalcogenide gave salts of the general formula Na [PhTE ], with T/E=Si/S (2); Si/Se (3); Sn/S (A); Sn/Se (4). Reaction of these salts with [Cu(PPh ) Cl] gave a series of organotetrel-copper chalcogenide clusters [(CuPPh ) (PhTE ) ] with T/E=Si/S; (5), Si/Se (6), Sn/S (7) and Sn/Se (8). Compounds 5-8 share a common structural motif with two intact {PhTE } units coordinating a Cu moiety, which was previously reported with other ligands, and for the Sn and Ge congeners only. If the Sn/Se reaction system was allowed to crystallize more slowly, single crystals of compound [(CuPPh ) (PhSnSe ) Cu SnSe] (9) were obtained, which are based on a larger cluster structure. Hence, 9 might form from 8 through incorporation of additional cluster fragments. The experimentally and quantum chemically determined optical properties were compared to related clusters.

摘要

通过加入相应的硫属化物钠，有机四价元素硫属化物杂金刚烷型簇合物[(PhT)E]（T/E = Si/S (1)；Si/Se；Sn/S和Sn/Se）发生碎片化反应，生成通式为Na[PhTE]的盐，其中T/E = Si/S (2)；Si/Se (3)；Sn/S (4)；Sn/Se (4)。这些盐与[Cu(PPh)Cl]反应，得到一系列有机四价元素 - 铜硫属化物簇合物[(CuPPh)(PhTE)]，其中T/E = Si/S (5)、Si/Se (6)、Sn/S (7)和Sn/Se (8)。化合物5 - 8具有共同的结构 motif，即两个完整的{PhTE}单元配位一个Cu部分，此前仅在其他配体以及Sn和Ge同系物的情况下有过报道。如果让Sn/Se反应体系更缓慢地结晶，则会得到化合物[(CuPPh)(PhSnSe)CuSnSe] (9)的单晶，其基于更大的簇结构。因此，9可能是由8通过并入额外的簇片段形成的。将实验测定和量子化学计算得到的光学性质与相关簇合物进行了比较。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/3b86a0b26b75/CHEM-27-11167-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/7444e082b12b/CHEM-27-11167-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/b2d98b3d6699/CHEM-27-11167-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/56763b612a5e/CHEM-27-11167-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/0a2b9bae5b34/CHEM-27-11167-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/da41866ead99/CHEM-27-11167-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/d4e6f2d21a69/CHEM-27-11167-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/3b7f1d536d94/CHEM-27-11167-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/79bb5d4c70aa/CHEM-27-11167-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/3b86a0b26b75/CHEM-27-11167-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/7444e082b12b/CHEM-27-11167-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/b2d98b3d6699/CHEM-27-11167-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/56763b612a5e/CHEM-27-11167-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/0a2b9bae5b34/CHEM-27-11167-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/da41866ead99/CHEM-27-11167-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/d4e6f2d21a69/CHEM-27-11167-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/3b7f1d536d94/CHEM-27-11167-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/79bb5d4c70aa/CHEM-27-11167-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cb8/8453927/3b86a0b26b75/CHEM-27-11167-g008.jpg

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