Synthesis and Characterization of a New Tiara Pd(II) Thiolate Complex, [Pd(SC₁₂H₂₅)₂]₆, and Its Solution-Phase Thermolysis to Prepare Nearly Monodisperse Palladium Sulfide Nanoparticles

Abstract

A new tiara Pd(II) thiolate complex, [Pd(SC12H25)2]6, has been synthesized and fully characterized by X-ray single crystal analysis, elemental analysis, MALDI, 1H NMR, powder XRD, IR, Raman, and UV/vis. It was found that, in each complex cluster, the six palladium atoms form a nearly planar hexagonal ring and the adjacent palladium atoms are bridged by sulfur atoms from both sides. Then the complex was further used as a single-source precursor to prepare nearly monodisperse palladium sulfide (PdS) nanoparticles through the high-temperature-induced decomposition in diphenyl ether. The obtained nanoparticles are 2.87 +/- 0.51 nm in diameter and protected by a layer of thiolate species on the surface.

Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

“…The Pd-S bond distances are within 2.305(2)-2.367(4) Å (average: 2.32(2) Å). The horizontal and vertical S-Pd-S bond angles vary between 93.50 (14) and 99.21 (8) located at axial and equatorial positions (i.e., the arms extend nearly perpendicularly and horizontally from the tiara ring), and some are significantly disordered; in particular, the axial arm on the S1 atom alternates between bending inward to occupy the inner void and extending out of the toroidal structure (~1:1). A similar inward curvature of an arm was also observed in [Ni(-SCH 2 CO 2 Et) 2 ] 8 .…”

“…8 Thiolate-bridged polynuclear group 10 transition-metal complexes with chain structures, [M(-SR) 2 ] n (M = Ni, Pd), have been investigated in detail because they provide efficient catalysis of atom-economical organic reactions such as regioselective additions of thiols and disulfides across alkynes. [8][9][10][11][12][13] Tiara-like complexes, which are also polynuclear group 10 transition-metal thiolates and are characterized by toroidal architectures, have been studied extensively, both in terms of their intriguing structural features and with respect to the preparation of monodisperse metal sulfide nanoparticles, 14 non-linear optical materials, 15 photoactive water-reducing catalysts, [16][17] and host-guest chemistry. 15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12].…”

“…15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12]. 15,[17][18][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] In contrast, although several tiara-like hexanuclear palladium complexes have been reported, 9,14,19,[36][37][38][39][40][41][42][43] only one octanuclear complex, i.e., [Pd(-S n Pr) 2 ] 8 , is known, and was obtained as a mixture with hexanuclear [Pd(-S n Pr) 2 ] 6 . 19 For platinum, infinite thiolates and selenolates [Pt(-ER) 2 ] ∞ (E = S, Se) have been synthesized using a solvothermal method; …”

Synthesis of palladium and palladium sulfide nanocrystals via thermolysis of a Pd–thiolate cluster

“…Its sulfides contain many kinds of compounds, including PdS, PdS 2 , Pd 3 S, Pd 16 S 7 , and Pd 4 S. PdS is a semiconductor with an energy gap about 2 eV which endows it applications in catalysis [40][41][42] and semiconductor materials science [43,44]. A classic way to synthesize metals or metal sulfides is thermal decomposition of the corresponding metal thiolates under solvents or solventless conditions [45][46][47]. Palladium and palladium sulfides can also be synthesized through thermolysis of palladium thiolate clusters [46,47] …”

“…A classic way to synthesize metals or metal sulfides is thermal decomposition of the corresponding metal thiolates under solvents or solventless conditions [45][46][47]. Palladium and palladium sulfides can also be synthesized through thermolysis of palladium thiolate clusters [46,47] …”