Synthesis, structure and properties of a novel iridium(III) pyrimidine complex

Triphenylphosphine-cyclometallated iridium(III) pyrimidine complexes: Synthesis, crystal structures and application in α-alkylation of ketones with alcohols

“…The synthetic routes to complexes 1e2 are depicted in Scheme 1.1 was prepared by reaction of Ir(III) Cl-bridged dimer [Ir(NDMP) 2 Cl] 2 [25] with PPh 3 according to the literature procedure [26]. 2 was also accessed by cyclometalation reaction of NDMP with IrCl 3 and PPh 3 [27].…”

“…The reaction is thought to proceed via the following three key steps: oxidation of the primary alcohol, base-catalyzed aldol condensation and selective hydrogenation of a,b-unsaturated ketones and esters. Based on these results and in connection with our experience in the synthesis and application of cyclometalated Ir(III) complexes [22,25], we were interested to see whether the obtained PPh 3 -cyclometalated Ir(III) complexes would be efficient catalysts for the a-alkylation of ketones with alcohols. Initially, the use of complex 2 as catalyst for the oxidation of benzyl alcohol was examined.…”

“…All other chemicals were commercially available expect for ligand NDMP and its cyclometalated Ir(III) Cl-bridged dimer [Ir(NDMP) 2 Cl] 2 which were prepared according to the published procedure [25]. Melting points were measured using a WC-1 microscopic apparatus and were uncorrected.…”

“…In recent years, part of our research effort has focused on the synthesis and application of cyclometalated complexes [22e24]. In a preliminary communication [25], we synthesized a new naphthalenylpyrimidine NDMP and its Ir(III) complexes. In view of these findings and our continuous interest in the synthesis and applications of other cyclometallated NDMP Ir(III) complexes, we prepared two PPh 3 -cyclometallated NDMP Ir(III) complexes Ir(NDMP) 2 PPh 3 Cl 1 and Ir(NDMP)(PPh 3 ) 2 Cl 2 2 and examined their catalytic activity in the a-alkylation of ketones with alcohols.…”

Crystal structure of 2-(2-naphthyl)-4,6-dimethylpyrimidine, C16H14N2

“…Thetitle compound was obtained from the coupling reaction of 2-naphthaleneboronic acid and 2-iodo-4,6-dimethylpyrimidine as described in literature [1]a nd recrystallized from dichloromethane/petroleum ether solution at room temperature to give the desired crystals suitable for single crystal X-ray diffraction.…”