Toward Permetalated Alkyne/Azide 3 + 2 or Click Cycloadducts Academic Article uri icon

abstract

  • The Cu(I)-catalyzed reaction of the platinum butadiynyl complex trans-(C 6F 5)(p-tol 3P) 2Pt(CC) 2H and rhenium cyclopentadienylazide complex ( 5- C 5H 4N 3)Re(CO) 3 yields the 1,2,3-triazole trans-(C 6F 5)(p-tol 3P) 2PtCCC=CHN(( 5-C 5H 4)Re(CO) 3)N=N (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-(C 6F 5)(p-tol 3P) 2PtCCC=CHN(CH 2C 6H 5)N=N and MeI gives an N(3)-methyl triazolium salt (81%), which upon addition of Ag 2O and [RhCl(cod)] 2 yields the N-heterocyclic carbene complex trans-(C 6F 5)(p-tol 3P) 2PtCCC ...C(RhCl(cod)) ...N(CH 2C 6H 5) ...N ...N(Me). Further experiments and analyses suggest that =CH derivatization is possible only when the 1H NMR chemical shift is downfield of ca. 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. 2012 American Chemical Society.

published proceedings

  • Organometallics

altmetric score

  • 0.25

author list (cited authors)

  • Clough, M. C., Zeits, P. D., Bhuvanesh, N., & Gladysz, J. A.

citation count

  • 37

complete list of authors

  • Clough, Melissa C||Zeits, Paul D||Bhuvanesh, Nattamai||Gladysz, John A

publication date

  • August 2012