Synthesis of a (N,C,C) Au(iii) pincer complex via C_sp3–H bond activation: increasing catalyst robustness by rational catalyst design

Abstract

A (N,CAr,CAlk) Au(iii) pincer complex has been synthesized from Au(OAc)3 (OAc = OCOCH3) and 2-(3,5-di-tert-butylphenyl)pyridine (L1) involving a Csp3-H bond activation by electrophilic substitution. In agreement with DFT calculations, the resulting complex significantly improves the performance of Au(tpy)(OAcF)2 (tpy = 2-(p-tolyl)pyridine, OAcF = OCOCF3) in the catalytic trifluoroacetylation of acetylene.

Tetradentate Gold(III) Complexes as Thermally Activated Delayed Fluorescence (TADF) Emitters: Microwave‐Assisted Synthesis and High‐Performance OLEDs with Long Operational Lifetime

“…Traditional synthesis via conventional heating has been attempted but failed to give the desired product. In light of the successful preparation of [Au(C^C^N)] complexes via the use of microwave irradiation, we then sought to achieve the last cyclometalation step with this method which was found to give the expected tetradentate Au III complexes in high yields (90 %). Regarding the design of the ligand, the placement of the aryloxy‐substituent on the 3‐position of the phenyl ring of C^N^C moiety allows the formation of 5‐5‐6‐membered chelate rings which may confer higher structural rigidity for minimizing k nr .…”

Advances and Prospects in Gold‐Catalyzed C−H Activation

“…Tilset et al . developed a new (N,C,C)‐Au(III) pincer complex 163 from Au(OAc) 3 and 2‐(3,5‐di‐ tert ‐butylphenyl)pyridine by both Csp 2 −H and Csp 3 −H bond activation (Scheme ) . They studied the activity of this complex in triflouroacetylation of acetylene.…”

“…They have applied this strategy to a wide variety of substrates in the presence of 10 mol% of gold catalyst 155 in DCE at room temperature affording good to excellent yields of the products. [37] They studied the activity of this complex in triflouroacetylation of acetylene. .…”

Synthesis of substituted (N,C) and (N,C,C) Au(iii) complexes: the influence of sterics and electronics on cyclometalation reactions

“…(N,C)-Cyclometalated Au(III) complexes [1][2][3][4] have found application within catalysis [5][6][7][8][9] and medicine [10][11][12][13][14][15] and have also gained attention for their photophysical properties. 3,4,[16][17][18] While cyclometalated Au(III) dichloro complexes have been known since the 1980s, 1 corresponding acetate and trifluoroacetate complexes are less studied.…”

“…[27][28][29] The scope of the microwave-assisted cyclometalation protocol has not been systematically investigated, although microwavemediated synthesis of Au(III) complexes has had an increase in popularity in the last decade. 3,[30][31][32][33][34][35][36] (N,C,C) Au(III) pincer complexes have been reported to be more stable than (N,C) systems towards protolytic decomposition, 8 and also possess interesting luminescence properties compared to (C,N,C) and (N,C) Au(III) complexes. 16 For Au(III), the majority of reported (N,C,C) pincer ligands are derived from 2-([1,1′-biphenyl]-3-yl)pyridine (Fig.…”