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铂末端聚乙炔基配合物-(CF)(-tolP)Pt(C≡C)H（= 2 - 4）与丁基锂的反应、Pt(C≡C)Li物种功能等效体的生成以及与有机和无机亲电试剂的衍生化反应

Reactions of Platinum Terminal Polyynyl Complexes -(CF)(-tolP)Pt(C≡C)H ( = 2-4) and -BuLi, Generation of Functional Equivalents of Pt(C≡C)Li Species, and Derivatization with Organic and Inorganic Electrophiles.

作者信息

Dey Baksi Sourajit, Aggrey Joshua O, Bhuvanesh Nattamai, Gladysz John A

机构信息

Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012, United States.

Department of Chemistry, East Tennessee State University, 1276 Gilbreath Drive, Johnson City, Tennessee 37614, United States.

出版信息

Organometallics. 2024 Apr 24;43(9):1041-1050. doi: 10.1021/acs.organomet.4c00098. eCollection 2024 May 13.

DOI:10.1021/acs.organomet.4c00098
PMID:38756992
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11094795/
Abstract

Reactions of the title complexes and -BuLi (1.5 equiv, -45 °C) afford functional equivalents of the deprotonated species -(CF)(-tolP)Pt(C≡C)Li ( = 2-4), as assayed by subsequent additions of MeI or MeSiCl to give -(CF)(-tolP)Pt(C≡C)Me (66-52%) or -(CF)(-tolP)Pt(C≡C)SiMe (63-49%). However, P NMR data suggest more complicated mechanistic scenarios, and small amounts of the hydride complex -(CF)(-tolP)PtH (independently synthesized from the chloride complex, AgClO, and NaBH) are detected in most cases. Analogous sequences involving -(CF)(-tolP)Pt(C≡C)H and benzyl bromide, DO, or W(CO)/MeO BF similarly afford products with Pt(C≡C)Bn, Pt(C≡C)D, or Pt(C≡C)C(OCH)=W(CO) linkages. The crystal structures of the tungsten and corresponding SiMe adduct, the three Pt(C≡C)Me species, and hydride complex are determined.

摘要

在-45℃下，标题配合物与叔丁基锂（1.5当量）反应，得到去质子化物种-（CF）（-tolP）Pt（C≡C）Li（=2-4）的功能等效物，通过随后加入甲基碘或甲基三氯硅烷进行测定，得到-（CF）（-tolP）Pt（C≡C）Me（66-52%）或-（CF）（-tolP）Pt（C≡C）SiMe（63-49%）。然而，磷核磁共振数据表明机理更为复杂，在大多数情况下检测到少量的氢化物配合物-（CF）（-tolP）PtH（由氯化物配合物、高氯酸银和硼氢化钠独立合成）。涉及-（CF）（-tolP）Pt（C≡C）H和苄基溴、重水或W（CO）/甲氧基三氟化硼的类似反应序列同样得到具有Pt（C≡C）Bn、Pt（C≡C）D或Pt（C≡C）C（OCH）=W（CO）键的产物。测定了钨和相应的甲基三氯硅烷加合物、三种Pt（C≡C）Me物种以及氢化物配合物的晶体结构。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/20ab87ae95a7/om4c00098_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/04fe31c08697/om4c00098_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/480d31147a75/om4c00098_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/5f8bccf62518/om4c00098_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/b55f36632395/om4c00098_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/cc38ea4ac435/om4c00098_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/ebadf4179998/om4c00098_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/20ab87ae95a7/om4c00098_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/04fe31c08697/om4c00098_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/480d31147a75/om4c00098_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/5f8bccf62518/om4c00098_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/b55f36632395/om4c00098_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/cc38ea4ac435/om4c00098_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/ebadf4179998/om4c00098_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e7e6/11094795/20ab87ae95a7/om4c00098_0008.jpg

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本文引用的文献

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