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 H, Weisbach N, Gauthier S, Kuhn H, Bhuvanesh N, Hampel F, Reibenspies JH, Gladysz JA (2021)
Publication Type: Journal article
Publication year: 2021
Journal
Abstract
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.
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APA:
Amini, H., Weisbach, N., Gauthier, S., Kuhn, H., Bhuvanesh, N., Hampel, F.,... Gladysz, J.A. (2021). 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. Chemistry - A European Journal. https://doi.org/10.1002/chem.202101725
MLA:
Amini, Hashem, et al. "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." Chemistry - A European Journal (2021).
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