Issue 36, 2021

SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions

Abstract

Combining strain-promoted azide–alkyne cycloaddition (SPAAC) and inorganic click (iClick) reactivity provides access to metal 1,2,3-triazolates. Experimental and computational insights demonstrate that iClick reactivity of the tested metal azides (LM-N3, M = Au, W, Re, Ru and Pt) depends on the accessibility of the azide functionality rather than electronic effects imparted by the metal. SPAAC iClick reactivity with cyclooctyne is observed when the azide functionality is sterically unencumbered, e.g. [Au(N3)(PPh3)] (Au–N3), [W(η3-allyl)(N3)(bpy)(CO)2] (W–N3), and [Re(N3)(bpy)(CO)3] [bpy = 2,2′-bipyridine] (Re–N3). Increased steric bulk and/or preequilibria with high activation barriers prevent SPAAC iClick reactivity for the complexes [Ru(N3)(Tp)(PPh3)2] [Tp = tris(pyrazolyl)borate] (Ru–N3), [Pt(N3)(CH3)(PiPr3)2] [iPr = isopropyl] (Pt(II)–N3), and [Pt(N3)(CH3)3]4 ((PtN3)4). Based on these computational insights, the SPAAC iClick reactivity of [Pt(N3)(CH3)3(P(CH3)3)2] (Pt(IV)–N3) was successfully predicted.

Graphical abstract: SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions

Supplementary files

Article information

Article type
Paper
Submitted
06 aug 2021
Accepted
09 aug 2021
First published
11 aug 2021

Dalton Trans., 2021,50, 12681-12691

Author version available

SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions

Y. Shen, A. M. Esper, I. Ghiviriga, K. A. Abboud, K. S. Schanze, C. Ehm and A. S. Veige, Dalton Trans., 2021, 50, 12681 DOI: 10.1039/D1DT02626G

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