Dicatenar pyridine-functionalised pyrazole ligands [Hpz(R(n,n)py)] (R(n,n) = C6H3(OCnH2n+1)2, n = 4, 6, 8, 10, 12, 14, 16, 18) have been strategically synthesised to be used as new building blocks for designing discotic liquid crystalline materials. Their coordination to Pd(II) fragments has allowed to achieve two novel families of metallomesogens, [Pd(pz(R(n,n)py))2] () and [PdCl2(Hpz(R(n,n)py...

Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-tempera...

The reactivity and stability of P(III)-N and P(III)≈N bonds will be different towards various solvents, bases, and acids because of their difference in bond strength due to different N-pπ-P-dπ donor bonding. For this, a P≈N containing Pd(II) complex, [Pd(DPAP)2] (C1), was synthesized from the reaction between PdCl2(COD) (COD = 1,4-cyclooctadiene) and 2 equiv. DPAP (diphenyl phosphino amino pyri...

Phosphinito-imines, a new class of P,N donors, are readily generated by reaction of bulky arylamide anions [RCONAr] (R = Me or t-Bu; Ar = 2,6-i-Pr2C6H4) with chlorophosphines ClP(R)2. In solution, free phosphinito-imines exist in equilibrium with the corresponding amidophosphine tautomers, containing a nitrogen-bound P(R)2 group. However, reacting the tautomer mixtures with metal precursor comp...

Group 3-15 metal chlorides (Lewis acids) were classified on the basis of activity and aldehyde- and aldimine-selectivity in an addition reaction of a silyl enol ether. Based on the experimental results, metal chlorides (Lewis acids) were classified as follows: A, active; B, weak; C, inactive for the activation of the aldehyde and/or aldimines. Groups A and B were further divided into A-1 or B-1...

An electrophilic substitution (SE) reaction of BN isosteres has been investigated for the dehydrogenation of ammonia borane (AB) by metal chlorides (MCl2) using various ab initio calculations. In contrast to the typical SE reaction occurring at the carbon atom, the nitrogen atom in AB serves as the reaction center for the SE reaction with the boron moiety as the leaving group when the MCl2 appr...

Coordination of an ambiphilic diphosphine-borane (DPB) ligand to the RhCl(CO) fragment affords two isomeric complexes. According to X-ray diffraction analysis, each complex adopts a square-pyramidal geometry with trans coordination of the two phosphine buttresses and axial RhB contacts, but the two differ in the relative orientations around the rhodium and boron centres. DFT calculations on the...

Modular fenchyl phosphinites (FENOPs) containing different aryl units-phenyl (1), 2-anisyl (2), or 2-pyridyl (3)-are efficiently accessible from (-)-fenchone. For comparison of the influence of the different aryl units on enantioselectivities and reactivities, these FENOPs were employed in Pd-catalyzed allylic alkylations. The strongly chelating character of P,N-bidentate 3 is apparent from X-r...

A new thiosemicarbazone (LH2) derived from indole-7-carbaldehyde was synthesized and reacted with Zn(II), Cd(II), Pd(II) and Pt(II) salts. The reactions with zinc and cadmium salts in 2 : 1 (ligand-metal) molar ratio afforded complexes of the type MX2(LH2)2, (X = Cl, Br or OAc), in which the thiosemicarbazone acts as a neutral S-monodentate ligand. In the presence of potassium hydroxide, the re...

Orthopalladation of the phenyl ring in the cyclopalladated complex [Pd{C,N-pyl-SCHC(O)Ph}(μ-X)]2 (pyl = 2-pyridyl, X = Cl; 1·Cl) occurs upon reacting it with AgOAc (1 : 2) in MeCN to give the pincer complex [Pd{C,C,N-pyl-SCHC(O)C6H4-2}(NCMe)] (2). The nature of the base and X plays a key role because palladation neither occurs with other bases nor when AgOAc is the base and X is Br, in which ca...