Toward Permetalated Alkyne/Azide 3+2 or "Click" Cycloadducts
Toward Permetalated Alkyne/Azide 3+2 or "Click" Cycloadducts
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DOI：
10.1021/om300542a
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发表时间：
2012-08-13
期刊：
影响因子：
2.8
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
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作者：
Clough, Melissa C.;Zeits, Paul D.;Gladysz, John A.
Cu(I) 催化的铂丁二炔基络合物反式-(C6F5)(p-tol(3)P)(2)Pt(C C)(2)H 和铼环戊二烯基叠氮络合物 (eta(5)-C5H4N3)Re(CO)(3) 反应生成 1,2,3-三唑trans-(C6F5)(p-tol(3)P)(2)PtC CC CHN(eta(5)-C5H4)Re(CO)(3))N N (54%)，用 Re-(CO)(5)OTf 或 Re(CO)(5)Br 处理后，得到 Re(CO)(5)+TfO- 或 cis-Re-(CO)(4)Br 加合物，这些加合物源自 N(3) 的攻击(84-98%)。比较了这三种配合物溶剂化物的晶体结构，但金属化 =CH 基团的尝试未成功。然而，单金属反式(C6F5)(p-tol(3)P)(2)PtC CC CHN(CH2C6H5)N=N和Mel的反应产生N(3)-甲基三唑鎓盐(81%)，在添加Ag2O和[RhCl(cod)](2)后产生N-杂环卡宾络合物反式-(C6F5)(p-tol(3)P)(2)PtC CC-C(RhCl(cod))-N(CH2C6H5)-N-N(Me)。进一步的实验和分析表明，只有当 H-1 NMR 化学位移位于约 100°C 的低场时，=CH 衍生化才有可能。增量 7.9 ppm。正电金属碎片通常会影响高场位移，这意味着将需要绝缘间隔物、负电配体和/或新的化学方法来通过点击化学构建四金属阵列。
The Cu(I)-catalyzed reaction of the platinum butadiynyl complex trans-(C6F5)(p-tol(3)P)(2)Pt(C C)(2)H and rhenium cyclopentadienylazide complex (eta(5)-C5H4N3)Re(CO)(3) yields the 1,2,3-triazole trans-(C6F5)(p-tol(3)P)(2)PtC CC CHN(eta(5)-C5H4)Re(CO)(3))N N (54%), which upon treatment with Re-(CO)(5)OTf or Re(CO)(5)Br affords Re(CO)(5)+TfO- or cis-Re-(CO)(4)Br adducts derived from attack at N(3) (84-98%). The crystal structures of solvates of these three complexes are compared, but attempts to metalate the =CH groups were unsuccessful. However, the reaction of monometallic trans(C6F5)(p-tol(3)P)(2)PtC CC CHN(CH2C6H5)N=N and Mel gives an N(3)-methyl triazolium salt (81%), which upon addition of Ag2O and [RhCl(cod)](2) yields the N-heterocyclic carbene complex trans-(C6F5)(p-tol(3)P)(2)PtC CC-C(RhCl(cod))-N(CH2C6H5)-N-N(Me). Further experiments and analyses suggest that =CH derivatization is possible only when the H-1 NMR chemical shift is downfield of ca. delta 7.9 ppm. Electropositive metal fragments generally effect upfield shifts, meaning that insulating spacers, electronegative ligands, and/or new chemical methodologies will be required to construct tetrametallic arrays via click chemistry.