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.

Autor: Amini H; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA., Weisbach N; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA., Gauthier S; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA., Kuhn H; Institut für Organische Chemie and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054, Erlangen, Germany., Bhuvanesh N; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA., Hampel F; Institut für Organische Chemie and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054, Erlangen, Germany., Reibenspies JH; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA., Gladysz JA; Department of Chemistry, Texas A&M University P.O. Box 30012, College Station, Texas, 77842-3012, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Sep 01; Vol. 27 (49), pp. 12619-12634. Date of Electronic Publication: 2021 Jul 13.
DOI: 10.1002/chem.202101725
Abstrakt: The silylated hexatriynyl complex trans-(C 6 F 5 )(p-tol 3 P) 2 Pt(C≡C) 3 SiEt 3 (PtC 6 TES) is converted in situ to PtC 6 H (wet n-Bu 4 N + F - , THF) and cross coupled with the diyne H(C≡C) 2 SiEt 3 (HC 4 TES; CuCl/TMEDA, O 2 ) to give PtC 10 TES (71 %). This sequence is repeated twice to afford PtC 14 TES (65 %) and then PtC 18 TES (27 %). An analogous series of reactions starting with PtC 8 TES gives PtC 12 TES (60 %), then PtC 16 TES (43 %), and then PtC 20 TES (17 %). Similar cross couplings with H(C≡C) 2 Si(i-Pr) 3 (HC 4 TIPS) give PtC 12 TIPS (68 %), PtC 14 TIPS (68 %), and PtC 16 TIPS (34 %). The trialkylsilyl species (up to PtC 18 TES) are converted to 3+2 "click" cycloadducts or 1,4-disubstituted 1,2,3-triazoles trans-(C 6 F 5 )(p-tol 3 P) 2 Pt(C≡C) n-1 C=CHN(CH 2 C 6 H 5 )N=N (29-92 % after workups). The most general procedure involves generating the terminal polyynes PtC x H (wet n-Bu 4 N + F - , THF) in the presence of benzyl azide in DMF and aqueous CuSO 4 /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 PtC 20 TES 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.
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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