Rhodium(III)-Catalyzed Hydroamination of Aromatic Terminal Alkynes with Anilines

Abstract

Society. It incorporates referee's comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document.

Cationic Rh and Ir complexes containing bidentate imidazolylidene–1,2,3-triazole donor ligands: synthesis and preliminary catalytic studies

“…7 The hydroamination of alkynes and alkenes is an atom economical method for the synthesis of C-N bonds and can be catalysed by lanthanides, actinides as well as early and late transition metal complexes. [8][9][10][11][12][13][14][15][16][17][18][19] Finding catalysts that are stable as well as effective for promoting a range of different hydroamination reactions remains an important challenge. Late transition metal complexes have lower oxophilicity and higher functional group tolerance in comparison to lanthanides, actinides and early transition metal complexes, and hence have great potential for a wider application as hydroamination catalysts.…”

The Reaction of [Cp*RhCl2]2, Aniline, and a Terminal Alkyne: Formation of Cyclometalated Rhodium(III) Complexes

“…5a-b,12 In an earlier study, we have found that [Cp*RhCl 2 ] 2 , 1 catalyses the hydroamination of terminal alkynes with anilines to afford ketimines. 13 Since 1 can effectively cyclometallate aromatic imines in the presence of acetate, we thought that the two separate steps may be combined to yield N-containing cyclometallated rhodium complexes in a single step. To the best of our knowledge, there is only one report of a similar strategy, which involves the single step synthesis of alkenyl ketone rhodium complexes using water and phenylacetylenes.…”

Synthesis of RhIII Anilido, Hydroxide, and Methoxide Complexes

“…A crystal structure of the Rh III aniline complex, [Cp*RhCl 2 (NH 2 Ph)] (Cp* = pentamethylcyclopentadienyl) has been reported 25. The Rh–N aniline bonds of complexes 1 [2.144(3) Å], 4 ‐OTf [2.120(9) and 2.132(8) Å], and 7 [2.117(3) Å] are slightly shorter than that of [Cp*RhCl 2 (NH 2 Ph)] [2.185(1) Å] 25.…”

“…A crystal structure of the Rh III aniline complex, [Cp*RhCl 2 (NH 2 Ph)] (Cp* = pentamethylcyclopentadienyl) has been reported 25. The Rh–N aniline bonds of complexes 1 [2.144(3) Å], 4 ‐OTf [2.120(9) and 2.132(8) Å], and 7 [2.117(3) Å] are slightly shorter than that of [Cp*RhCl 2 (NH 2 Ph)] [2.185(1) Å] 25. The N–C ipso bond length of [Cp*RhCl 2 (NH 2 Ph)] [1.446(2) Å]25 is of a similar magnitude to those of the complexes reported herein [ 1 , 1.429(5) Å; 4 ‐OTf, 1.44(2) and 1.46(2) Å; and 7 , 1.443(4) Å].…”

“…The Rh–N aniline bonds of complexes 1 [2.144(3) Å], 4 ‐OTf [2.120(9) and 2.132(8) Å], and 7 [2.117(3) Å] are slightly shorter than that of [Cp*RhCl 2 (NH 2 Ph)] [2.185(1) Å] 25. The N–C ipso bond length of [Cp*RhCl 2 (NH 2 Ph)] [1.446(2) Å]25 is of a similar magnitude to those of the complexes reported herein [ 1 , 1.429(5) Å; 4 ‐OTf, 1.44(2) and 1.46(2) Å; and 7 , 1.443(4) Å]. The C ipso –N–Rh bond angle of [RhCp*Cl 2 (NH 2 Ph)] [122.74(9)°]25 is larger than that of complexes 1 [119.4(2)°], 4 ‐OTf [120.1(7) and 118.2(6)°], and 7 [119.2(2)°], perhaps on account of the different ligand set on Rh.…”