Single-crystal EPR studies on nickel(III), palladium(III), and platinum(III) dithiolene chelates containing the ligands isotrithionedithiolate, o-xylenedithiolate, and maleonitriledithiolate

The Chemistry of Gold

“…Homoleptic gold(III) derivatives with dithiolate, ligands of the type [Au(S-S) 2 ] À are well known and are usually prepared from [AuCl 4 ] À with the dithiol; some examples are with 1,2-benzene dithiolate, maleonitriledithiolate, dmit, and so on, [164,336]. Similar complexes have been reported for bidentate sulfur ligands such as dithiocarbamates, dithiophosphates, and so on, [41].…”

Ligand Radicals as Modular Organic Electron Spin Qubits

“…[27,31] Here, with an unpaired electron predominantly on the ligand, the metal ion presentsaheavy-atom effect, ap henomenon that has been exploited in ar ange of materials, most notably enhancing the performance of semiconductors in spintronic devices. [32] At the measurement temperature, ad irect spin relaxation process is dominant, [33] but as the temperature increases the Raman mechanism takes precedence [34] and becomes more efficient with increasing SOC. [35] While relaxation times cannotb ed irectly computed, we have used the calculated electronic structure parameters to estimate T 1,s for 1 and 2 when compared to that for 3.T his estimate uses the ratio of the SOC constant for Ni and Pd to that for Pt, and the parentage of the spin in the molecule that resides on the metal ion ( Table 1).…”

Palladium(III) in Synthesis and Catalysis

“…The polyatomic anions PdF 4 − and PdF 6 3− have been prepared by solid-state synthesis [20-22]. Mononuclear coordination complexes containing Pd(III) have been observed by electrochemical measurements as well as EPR spectroscopy [23-30], although assignment of these complexes as containing Pd(III), and not Pd(II) with a singly oxidized ligand framework, has been the source of continuing discussion [31-34]. In 2010, the (+III) oxidation state of Pd was stabilized in a mixed Ni/Pd oligomeric M–X–M–X chain of the formulation [Ni 1-x Pd x (chxn)Br]Br 2 (chxn = (1 R ,2 R )-cyclohexanediamine) by electrochemical oxidation of a mixture of [Ni(chxn) 2 ]Br 2 and [Pd(chxn) 2 ]Br 2 [35,36].…”