Luminescent diphosphine dithiolate complexes of platinum(II): synthesis, characterization, and structure

Abstract

The synthesis, characterization, and emission properties of a series of Pt(diphosphine)(dithiolate) complexes are reported. Diphosphine ligands include l,2-bis(diphenylphosphino)ethane(dppe), l,2-bis(diphenylphosphino)ethylene (dppv), l,2-bis(diphenylphosphino)benzene (dppb), l,2-bis(dicyclohexylphosphino)ethane (chpe), bis(diphenylphosphino)methane (dppm), l,2-bis(dimethoxyphosphino)ethane (pompom), triphenylphosphine (PPh3), dimethylphenylphosphine (PMe2Ph), tricyclohexylphosphine (PCy3), triphenyl phosphite (P(OPh)3), and triisopropyl phosphite (P( 0-/-Pr)3). Dithiolate ligands include maleonitriledithiolate (mnt) and l-(ethoxycarbonyl)-l-cyanoethylene-2,2-dithiolate (ecda). The complexes are readily synthesized by the addition of the diphosphine ligand to Pt-(COD) (dithiolate). On the basis of characterizations using NMR and infrared spectroscopies, all of the complexes are assigned square planar coordination geometries with varying degrees of distortion determined by ligand steric and electronic effects. The assignment of square planar coordination is confirmed by single crystal structure

Reaction of the Tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) with Activated Alkynes to Form Dithiolenes and Diselenolenes

“…The Pt-P distances in 2b (2.268, 2.265 Å ) may be compared with those in [Pt{S 2 C 2 S 2 CS}(dppe)] (2.258, 2.250 Å ) [21] and [Pt{S 2 C 2 (CN) 2 }(dppe)] (2.262, 2.252 Å ). [22] Comparable Pt-S distances to those in 2b (2.297, 2.318 Å ) are found in [Pt{S 2 C 2 (CO 2 Me) 2 }{P(OMe) 3 } 2 ] (2.300, 2.302 Å ) [23] and [Pt{S 2 C 2 (CO 2 Me) 2 }(PPh 3 ) 2 ] (2.304 Å ). [12] Crystals of 3b suitable for study by X-ray diffraction could not be obtained.…”

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

“…Figure 11 shows the linear correlation between ModEP and the computed ω; a good correlation coefficient is found (R 2 = 0.92), and Equation (27) is obtained. ModEP = 1.151 ω -3.085 (27) Thus, both ModEP and ω can find application as quantitative indices of a ligand's electronic behavior. The great advantage of ω is that it can be easily calculated for a broad range of ligand types.…”

Bis(hydrosulfido)-bridged dinuclear rhodium(i) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru)

“…The chemistry of transition metal sulfido clusters has been attracting significant attention because of their relation to the 25 active sites of certain metalloenzymes and industrial metal sulfide catalysts for hydrotreating processes. 1 The development of rational synthetic methods has allowed for the preparation of a wide range of multimetallic cores with bridging sulfido ligands having the desired metal composition and metal-sulfur 30 framework.…”

“…Although a triangular structure with a bridging chlorido ligand at one of the Rh-Ir edges would fulfill the symmetry requirements, it would result in a 18 e -Rh(I) centre. Taking into account that the equivalent P(OPh) 3 ligands in 5 were observed at similar chemical shift and comparable J Rh-P coupling 25 constant that those of 4 (4, 117.24 ppm, J Rh-P = 293 Hz; 5, 121.54 ppm, J Rh-P = 290 Hz), the more likely structure should have a Cp*IrCl fragment with a terminal chlorido ligand, although a weak interaction with the adjacent rhodium centre can not be excluded. 4 ] obtained by thermolysis of a triangular RhRe 2 cluster in the presence of H 2 S (g).…”

“…In the case of 9, data were collected in the single axis HUBER diffractometer of the BM16 CRG beamline at the 25 ESRF. Data were measured in all cases at low temperature (100(2) K) and using graphite-monochromated Mo-Kα radiation (λ = 0.710 73 Å) for those crystals measured at local diffractometers or using Silicon(111) monochromated synchrotron radiation for 9 (λ = 0.73820 Å).…”