作者:Melissa C. Clough、Paul D. Zeits、Nattamai Bhuvanesh、John A. Gladysz
DOI:10.1021/om300542a
日期:2012.8.13
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.