Toward Permetalated Alkyne/Azide 3 + 2 or “Click” Cycloadducts
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https://figshare.com/articles/dataset/Toward_Permetalated_Alkyne_Azide_3_2_or_Click_Cycloadducts/2497303
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资源简介：
The Cu(I)-catalyzed reaction of the platinum butadiynyl
complex trans-(C6F5)(p-tol3P)2Pt(CC)2H and rhenium cyclopentadienylazide complex (η5-C5H4N3)Re(CO)3 yields the 1,2,3-triazole trans-(C6F5)(p-tol3P)2PtCCCCHN((η5-C5H4)Re(CO)3)NN (54%), which upon treatment with Re(CO)5OTf
or Re(CO)5Br affords Re(CO)5+TfO– or cis-Re(CO)4Br 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-tol3P)2PtCCCCHN(CH2C6H5)NN and
MeI 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-tol3P)2PtCCC...C(RhCl(cod))...N(CH2C6H5)...N...N(Me). Further
experiments and analyses suggest that CH derivatization is
possible only when the 1H NMR chemical shift is downfield
of ca. δ 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.
创建时间：
2012-08-13
