Synthesis, Characterisation, and X‐ray Crystal Structure of New Ni^II, Pd^II, and Pt^II Complexes of Tridentate Pyrazole‐Based Ligands with an NOS‐Donor Set

Unexpected formation of [Pd(bedp)][Pd2Cl4(μ-SMe)2] (bedp = 1,4-bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]piperazine). Structural characterisation and spectroscopic properties

“…In our group, we have studied the coordinative properties of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole towards group 10 metal salts yielding [MCl(l-med)] 2 (M = Ni(II), Pd(II), Pt(II)) [8]. The reaction of the complex [PdCl(l-med)] 2 with pyridine (py) or PPh 3 produces complexes [Pd(l-med)(L)] 2 (BF 4 ) 2 (L = py or PPh 3 ) [9].…”

“…The reaction of the complex [PdCl(l-med)] 2 with pyridine (py) or PPh 3 produces complexes [Pd(l-med)(L)] 2 (BF 4 ) 2 (L = py or PPh 3 ) [9].…”

“…In these reactions, the ligands form, with Pd(II), mononuclear compounds [Pd(NN 0 N 0 N)]X 2 (X À = Cl À or BF À 4 ), and dinuclear compounds [Pd 2 Cl 4 (NN 0 N 0 N)] [5]. These two ligands had previously been described by Driessen et al [6].On the other hand, the coordination chemistry of transitionmetalthiolate complexes has been actively pursued in the past several years, motivated primarily by the bonding diversity, potential use as precursors to new solid-state materials, and the relevance of such complexes to biomimetic chemistry [7].In our group, we have studied the coordinative properties of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole towards group 10 metal salts yielding [MCl(l-med)] 2 (M = Ni(II), Pd(II), Pt(II)) [8]. The reaction of the complex [PdCl(l-med)] 2 with pyridine (py) or PPh 3 produces complexes [Pd(l-med)(L)] 2 (BF 4 ) 2 (L = py or PPh 3 ) [9].…”

A Theoretical Study on PdIIComplexes Containing Hemilabile Pyrazole‐Derived Ligands

“…[13] In recent years our research group has reported the synthesis, the characterization and the coordinating properties of pyrazolic ligands containing additional donor groups: N,N, [14] N,O, [15] N,P [16] and N,S. [17] NMR studies of complexes in solution have shown that some of them display hemilability; pyrazole is the stronger (inert) donor group, except in the case of N,P and N,S for which it can also behave as a labile group. Previous studies with Pz-(CH 2 ) x S(CH 2 ) y S(CH 2 ) x -Pz tetradentate ligands and Pd II have shown that both N,N bicoordination and N,S,S,N tetracoordination are obtained and can be interconverted in solution (see Scheme 2).…”

Synthesis and characterization of silver(I) complexes [AgL]2[BF4]2 and [Ag(OAc)L]∞ [L=(CH2NHCOC2H4PPh2)2]

“…X-ray crystallographic studies showed that the ligand adopts a linear conformation in dimeric complex 1 and a bent conformation in polymeric complex 2. Both compounds exhibited temperature-dependent 31 P{ 1 H} NMR spectra.In recent years there has been considerable interest in the use of so-called hemilabile ligands, which containing two or more possible chelating sites of differing donor ability [1][2][3]. These systems are interesting due to the different reactivities of the two types of donor atom in the ligand, which leads them to application in catalysis, because the labile center can readily dissociate from the metal, thus facilitating a vacant coordinating site that can produce an active intermediate for catalysis [4][5][6].…”