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  • Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination.

Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination.

Science (New York, N.Y.) (2019-09-14)
Kurtis M Carsch, Ida M DiMucci, Diana A Iovan, Alex Li, Shao-Liang Zheng, Charles J Titus, Sang Jun Lee, Kent D Irwin, Dennis Nordlund, Kyle M Lancaster, Theodore A Betley
ABSTRACT

Terminal copper-nitrenoid complexes have inspired interest in their fundamental bonding structures as well as their putative intermediacy in catalytic nitrene-transfer reactions. Here, we report that aryl azides react with a copper(I) dinitrogen complex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrene complexes with near-linear, short copper-nitrenoid bonds [1.745(2) to 1.759(2) angstroms]. X-ray absorption spectroscopy and quantum chemistry calculations reveal a predominantly triplet nitrene adduct bound to copper(I), as opposed to copper(II) or copper(III) assignments, indicating the absence of a copper-nitrogen multiple-bond character. Employing electron-deficient aryl azides renders the copper nitrene species competent for alkane amination and alkene aziridination, lending further credence to the intermediacy of this species in proposed nitrene-transfer mechanisms.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Luperox® DI, tert-Butyl peroxide, 98%
Sigma-Aldrich
Copper(II) chloride, anhydrous, powder, ≥99.995% trace metals basis
Sigma-Aldrich
2-Ethyl-1-butene, 95%
Sigma-Aldrich
Butyl isocyanide, 97%