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锝和铼的亚硝酰基及硫代亚硝酰基配合物及其与三（吡唑基）硼酸氢盐的反应

Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.

作者信息

Sawallisch Till Erik, Abdulkader Abdullah, Nowak Domenik, Hagenbach Adelheid, Abram Ulrich

机构信息

Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany.

出版信息

Molecules. 2024 Aug 15;29(16):3865. doi: 10.3390/molecules29163865.

DOI:10.3390/molecules29163865
PMID:39202944
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11357682/
Abstract

The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [Tc(NS)Cl(PPh)] () and [Tc(NS)Cl(PPh)(OPPh)] () and their reaction products with hydrotris(pyrazolyl)borates, {HB(pz)}. Similar reactions were conducted with [Tc(NO)Cl(PPh)(CHCN)] and related rhenium thionitrosyls. Remarkably, most such reactions result in a rapid cleavage of the boron-nitrogen bonds of the ligands and the formation of pyrazole complexes of the two group 7 metals. Only one compound with an intact {HB(pz)} ligand could be isolated: the technetium(I) complex [Tc(NO)Cl(PPh){HB(pz)}] (). Other products show the coordination of one or four neutral pyrazole ligand(s) in the coordination spheres of technetium generated by thermal decomposition of the pyrazolylborates [Tc(NO)Cl(PPh)(pz)] () and [Tc(NS)Cl(pz)] (). Reactions with the corresponding thionitrosylrhenium complex [Re(NS)Cl(PPh)] require higher temperatures and only compounds with one pyrazole ligand, [Re(NS)Cl(PPh)(pz)] (-), were isolated. The products were studied spectroscopically and by X-ray diffraction.

摘要

通过合成[Tc(NS)Cl(PPh₃)]（）和[Tc(NS)Cl(PPh₃)(OPPh₃)]（）及其与氢化三（吡唑基）硼酸盐{HB(pz)₃}的反应产物，增加了结构已知的锝硫代亚硝基配合物的数量。对[Tc(NO)Cl(PPh₃)(CH₃CN)]和相关铼硫代亚硝基配合物进行了类似反应。值得注意的是，大多数此类反应会导致配体的硼氮键迅速断裂，并形成两种第7族金属的吡唑配合物。仅分离出一种具有完整{HB(pz)₃}配体的化合物：锝（I）配合物[Tc(NO)Cl(PPh₃){HB(pz)₃}]（）。其他产物显示，通过吡唑基硼酸盐[Tc(NO)Cl(PPh₃)(pz)]（）和[Tc(NS)Cl(pz)]（）的热分解在锝的配位球中形成了一个或四个中性吡唑配体的配位。与相应的硫代亚硝基铼配合物[Re(NS)Cl(PPh₃)]的反应需要更高的温度，并且仅分离出具有一个吡唑配体的化合物[Re(NS)Cl(PPh₃)(pz)]（-）。通过光谱学和X射线衍射对产物进行了研究。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/eb24a9b7f412/molecules-29-03865-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/5c3b48d166d8/molecules-29-03865-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/bbc20a1fbc47/molecules-29-03865-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/3950dccf518c/molecules-29-03865-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/4cbc96a5e45e/molecules-29-03865-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/532f8ebe11ee/molecules-29-03865-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/e72856e1379c/molecules-29-03865-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/053f70d4fdea/molecules-29-03865-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/bfa7e1df5b91/molecules-29-03865-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/e072aaaca2d0/molecules-29-03865-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/d4bd8ed83018/molecules-29-03865-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/eb24a9b7f412/molecules-29-03865-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/5c3b48d166d8/molecules-29-03865-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/bbc20a1fbc47/molecules-29-03865-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/3950dccf518c/molecules-29-03865-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/4cbc96a5e45e/molecules-29-03865-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/532f8ebe11ee/molecules-29-03865-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/e72856e1379c/molecules-29-03865-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/053f70d4fdea/molecules-29-03865-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/bfa7e1df5b91/molecules-29-03865-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/e072aaaca2d0/molecules-29-03865-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/d4bd8ed83018/molecules-29-03865-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/23d8/11357682/eb24a9b7f412/molecules-29-03865-g007.jpg

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