Both neutral and cationic iridium(III) complexes containing carborane units were synthesized. Bulky carboranes can significantly improve phosphorescence quantum yields of these complexes and the electronic effect of carboranes can evidently tune emission wavelengths of cationic complexes.

One-pot synthesis: An efficient amino-directed one-pot synthesis of N-H carbazoles from unprotected 2-aminobiaryl compounds is reported. The free amino unit acts as both a directing group for ortho C-H activation and a functional group for construction of an N-heterocyclic ring (see scheme).

The reactions of the 16e half-sandwich complex, CpCo(S(2)C(2)B(10)H(10)) (1), with alkynones at ambient temperature lead to complexes CpCo(S(2)C(2)B(10)H(9))(CH=CH-C(O)R) (R = Ph (2), 2-naphthyl (3)). Both 2 and 3 are still 16e half-sandwich complexes containing a B(3)-substituted ortho-carborane-1,2-dithiolate ligand. Treatment of 2 with excess alkynes R(1)C[triple bond]CR(2) (R(1) = H, R(2) = Ph, C(O)Ph, CO(2)Me; R(1) = R(2) = CO(2)Me) affords five complexes, CpCo(S(2)C(2)B(10)H(8))(CH(2)CPh)(CH=CH-C(O)Ph) (4), CpCo(S(2)C(2)B(10)H(8))(CH=CH-C(O)Ph)(2) (5), CpCo(S(2)C(2)B(10)H(8))(CH=CH-CO(2)Me)(CH=CH-C(O)Ph) (6), CpCo(S(2)C(2)B(10)H(9))(MeO(2)C-C=C-CO(2)Me)(CH=CH-C(O)Ph) (7), and CpCo(S(2)C(2)B(10)H(9))(MeO(2)C-C=C-CO(2)Me)(2)(CH=CH-C(O)Ph) (8). Complex 4 is an 18e complex bearing a B-CH(2) unit. Both 5 and 6 retain a 16e half-sandwich structure but contain a B(3,6)-disubstituted ortho-carborane-1,2-dithiolate ligand. However, in 7 and 8 one or two alkynes are inserted into one of the Co-S bonds to generate 18e species, respectively. Heating 7 leads to the 16e complex, CpCo(S(2)C(2)B(10)H(8))(MeO(2)C-C=CH-CO(2)Me)(CH=CH-C(O)Ph) (9), having a B(3,6)-disubstituted ortho-carborane-1,2-dithiolate ligand as in 5 and 6. All complexes were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 2 and 3 and 5-9 were further characterized by X-ray structural analysis.

Nitro compounds are important intermediates in synthetic organic chemistry and the chemical industry. Herein, the efficient copper-catalyzed [10 % Cu(NO 3 ) 2 ·3H 2 O] nitration of anilides was developed by using TBN (tert-butyl nitrite) as a nitrating reagent to give the corresponding nitro-substituted aromatic products in good to excellent yields. The use of TBN also led to the selective nitration of acrylamides at room temperature to afford only the (E) isomer of the nitration product.[a] State Key A series of anilides and acrylamides with a broad array of functional groups were well-tolerated by this procedure. This synthetic method has many advantages, which include inexpensive starting materials, mild reaction conditions, a fast reaction rate, and high yields. A mechanistic investigation indicates that a nitro radical, which is generated from the thermal homolysis of TBN, is involved in the two nitration processes.www.eurjoc.org