Towards the rational design of ylide-substituted phosphines for gold(i)-catalysis: from inactive to ppm-level catalysis.

The implementation of gold catalysis into large-scale processes suffers from the fact that most reactions still require high catalyst loadings to achieve efficient catalysis thus making upscaling impractical. Here, we report systematic studies on the impact of the substituent in the backbone of ylide-substituted phosphines (YPhos) on the catalytic activity in the hydroamination of alkynes, which allowed us to increase the catalyst performance by orders of magnitude. While electronic changes of the ligand properties by introduction of aryl groups with electron-withdrawing or electron-donating groups had surprisingly little impact on the activity of the gold complexes, the use of bulky aryl groups with ortho-substituents led to a remarkable boost in the catalyst activity. However, this catalyst improvement is not a result of an increased steric demand of the ligand towards the metal center, but due to steric protection of the reactive ylidic carbon centre in the ligand backbone. The gold complex of the thus designed mesityl-substituted YPhos ligand YMesPCy2, which is readily accessible in one step from a simple phosphonium salt, exhibited a high catalyst stability and allowed for turnover numbers up to 20 000 in the hydroamination of a series of different alkynes and amines. Furthermore, the catalyst was also active in more challenging reactions including enyne cyclisation and the formation of 1,2-dihydroquinolines.

Photoluminescent calcium azolium carboxylates with diversified calcium coordination geometry and thermal stability.

Despite the popularity and versatility of transition-metal­azolium carboxylate coordination polymers, there are very few examples of group 2 complexes supported by azolium carboxylate ligands in the literature, and there are none featuring luminescent calcium azolium carboxylates. New ionic calcium coordination networks, {[Ca2(L(1))2(H2O)4](Br)4·6H2O}∞ (1), {[(L(3))2Ca(H2O)2]2(Br)2}∞ (3), {[(L(4))2Ca(H2O)2]2(Br)2}∞ (4), and {[(L(5))2Ca3(Na)(H2O)9(Cl)](Br)6·2H2O}∞ (5) along with binuclear {[Ca2(L(2))2(H2O)9](Br)4·4H2O} (2), and trinuclear {[(L(6))2Ca3(H2O)9](Br)6} (6) were isolated from the reaction between the corresponding azolium carboxylates and calcium carbonate in aqueous solution. 1­6 were characterized by FT-IR, NMR, TGA, UV-vis, fluorescence and single crystal X-ray diffraction techniques. Interestingly, the first tetra-cationic binuclear calcium 2 was isolated using L(2)H2Br2 and hexa-cationic trinuclear calcium 6 was isolated using L(6)H3Br3. The 3D coordination polymers 1 and 4 were derived with the help of L(1)H2Br2 and L(4)H2Br2, respectively, through Br···H hydrogen bonding. The 3D MOF 3 with rhomboidal channels was constructed using L(3)H2Br2, where the channel size is about 4.8 × 2.9 nm. 5 was isolated as a rare 1D coordination polymer. The choice of azolium carboxylates in these solids not only changes the topology of the network but also affects the chemistry exhibited by the network. Calcium azolium carboxylate assemblies 1­4 and 6 exhibit interesting solid-state photoluminescence properties, driven by azolium carboxylate ligands. Variation of the bridging chromophore produced significant effects on the fluorescence properties. 1­4 and 6 represent the first examples of luminescent calcium azolium carboxylate complexes. As can be seen in the six metal­organic assemblies presented in this report, a combination of carboxylate groups and steric hindrance affects the topology and physical properties of the resultant solids.