Cyclopalladated compounds with bridging and chelating diphosphine ligands. Effect of ring size. Crystal and molecular structure of [{Pd[4-(COH)C6H3C(H)N(Cy)-C2,N](Cl)}2(μ-Ph2PCH2PPh2)]

New developments in the studies of the reactivity of cyclometallated palladium(II) compounds with homo- ([P,P],[As,As]) and heterobidentate ([P,N],[P,O]) ligands

“…Tetradentate [C,N,C,N] Schiff bases generally undergo double metallation to give compounds with two metal atoms per organic ligand [6][7][8][9][10][11][12][13][14][15][16], however, as we have reported previously, in the case of the potentialy tetradentate ligands derived from isophthalaldehyde, 1,3-(CyN@CH) 2 C 6 H 4 , and terephthalaldehyde, 1,4-(CyN@CH) 2 conditions [17][18][19]. Thus, treatment with palladium(II) acetate in acetic acid gave the monocyclometallated complexes 1 and 2 after cleavage of one C@N double bond, and we have studied the reactivity of these cyclometallated complexes towards different mono and bidentate ligands [20][21][22][23][24]. Herein, we present further developments of our investigations regarding the reactivity of 1 and 2 with the new group 15 donor atom bidentate ligands: the diphosphines, 1,2-bis(di-o-tolylphosphino)ethane and 4-(diphenylphosphino)-2-(diphenylphosphinomethyl)pyrrol, as well the diarsine: 1,2-bis(diphenylarsino)ethane.…”

“…Treatment of 1 and 2 with Ph 2 P(C 6 H 4 )CHO in a 1:2 molar ratio in the presence of NH 4 Suitable crystals were grown by slowly evaporating dichloromethane/n-hexane (7,15,21) or chloroform/n-hexane (11) solutions of the complexes. The labeling schemes for the compounds are shown in Figs.…”

“…The crystal structures of compounds 11, 15 and 21 comprise a mononuclear cation (one molecule per asymmetric unit), a perchlorate (15) or a hexafluorophosphate (11,21) anion, 1.25CHCl 3 for 11, and half molecule of CH 2 Cl 2 for 15.…”

Synthesis, characterization and crystal structures of cyclometallated palladium (II) compounds containing difunctional ligands with [P,P], [As,As], [N,N], [P,As], [P,N] and [P,O] donor atoms

“…In the past we have researched the reactivity of cyclometallated compounds with diphosphines, due to the versality of the electronic and steric properties of the latter [5][6][7][8][9]; more recently we have prepared a series of related complexes with diarsines [10]. We were now interested in looking further into the chemistry of cyclopalladated complexes when they react with other bidentate group 15 donor atom ligands such as diamines.…”

Novel cyclometallated Pd(II) and Pt(II) complexes with indole derivatives and their use as catalysts in Heck reaction

“…Many useful applications of cyclometallated compounds in organic chemistry are well established, e.g., to the synthesis of heterocycles and of enantiomerically enriched molecules, to prepare liquid crystals (metallomesogens) [2], to the resolution of racemates and to the evaluation of optical purity [3]. Finally, they have proved useful in the design of molecules with promising photochemical [4] and anticancer properties [5]. Cyclometallated compounds are organometallic complexes embodying an E-M-C connectivity of r-bonds, where E is a heterodonor atom of the 15-or 16-group, M a metallic atom and C a carbon donor.…”