1192358-85-2Relevant academic research and scientific papers
Trapping of Terminal Platinapolyynes by Copper(I) Catalyzed Click Cycloadditions; Probes of Labile Intermediates in Syntheses of Complexes with Extended sp Carbon Chains, and Crystallographic Studies
Amini, Hashem,Bhuvanesh, Nattamai,Gauthier, Sébastien,Gladysz, John A.,Hampel, Frank,Kuhn, Helene,Reibenspies, Joseph H.,Weisbach, Nancy
supporting information, p. 12619 - 12634 (2021/07/20)
The silylated hexatriynyl complex trans-(C6F5)(p-tol3P)2Pt(C≡C)3SiEt3 (PtC6TES) is converted in situ to PtC6H (wet n-Bu4N+ F?, THF) and cross coupled with the diyne H(C≡C)2SiEt3 (HC4TES; CuCl/TMEDA, O2) to give PtC10TES (71 %). This sequence is repeated twice to afford PtC14TES (65 %) and then PtC18TES (27 %). An analogous series of reactions starting with PtC8TES gives PtC12TES (60 %), then PtC16TES (43 %), and then PtC20TES (17 %). Similar cross couplings with H(C≡C)2Si(i-Pr)3 (HC4TIPS) give PtC12TIPS (68 %), PtC14TIPS (68 %), and PtC16TIPS (34 %). The trialkylsilyl species (up to PtC18TES) are converted to 3+2 “click” cycloadducts or 1,4-disubstituted 1,2,3-triazoles trans-(C6F5)(p-tol3P)2Pt(C≡C)n-1C=CHN(CH2C6H5)N=N (29–92 % after workups). The most general procedure involves generating the terminal polyynes PtCxH (wet n-Bu4N+ F?, THF) in the presence of benzyl azide in DMF and aqueous CuSO4/ascorbic acid. All of the preceding complexes are crystallographically characterized and the structural and spectroscopic properties analyzed as a function of chain length. Two pseudopolymorphs of PtC20TES are obtained, both of which feature molecules with parallel sp carbon chains in a pairwise head/tail packing motif with extensive sp/sp van der Waals contacts.
Toward permetalated alkyne/azide 3 + 2 or "click" cycloadducts
Clough, Melissa C.,Zeits, Paul D.,Bhuvanesh, Nattamai,Gladysz, John A.
, p. 5231 - 5234 (2012/11/07)
The Cu(I)-catalyzed reaction of the platinum butadiynyl complex trans-(C6F5)(p-tol3P)2Pt(C≡C) 2H and rhenium cyclopentadienylazide complex (η5- C5H4N3)Re(CO)3 yields the 1,2,3-triazole trans-(C6F5)(p-tol3P) 2PtC≡CC=CHN((η5-C5H 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-(C6F 5)(p-tol3P)2PtC≡CC=CHN(CH 2C6H5)N=N 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-(C 6F5)(p-tol3P)2PtC≡CC ...C(RhCl(cod))...N(CH2C6H 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. 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.
"Click" chemistry in metal coordination spheres: Copper(I)-catalyzed 3+2 cycloadditions of benzyl azide and platinum polyynyl complexes trans-(C6F5)(p-tol3P) 2Pt(C≡C)nH (n = 2-6)
Gauthier, Sebastien,Weisbach, Nancy,Bhuvanesh, Nattamai,Gladysz, John A.
, p. 5597 - 5599 (2010/01/06)
Summary; Benzyl azide and the terminal polyynyl complexes trans-(C 6F5)(p-tol3P)2Pt(C≡C) nH(n = 2-6) undergo 3+2 "click" cycloadditions in the presence of CuSO4/ascorbic acid to give the 1,
