Synthetic routes to tetrathiometalate complexes of rhodium, iridium, palladium, and platinum are described. Acetonitrile solutions of WS42- reacted with [Rh(diene)Cl]2 (where diene = 1,5-cyclooctadiene (COD) or norbornadiene (NBD)), [Ir(COD)Cl]2, [(η5-C5Me5)RhCl2]2, and [Pd(allyl)Cl]2 to give good yields of μ-WS4 complexes [Rh(diene)]2WS4, [Ir(COD)]2WS4, [(η5-C5Me5)RhCl]2WS4, and [(allyl)Pd]2WS4, respectively. (COD)PtCl2 reacted with MS42- to give (COD)PtMS4, M = Mo, W. The latter complexes react further with PPh3 or WS42- to give (PPh3)2PtMS4 and Pt(WS4)22-, respectively. [Rh(COD)]2WS4 reacted with t-BuNC to give [Rh(t-BuNC)2]2WS4. RhCl3·3H2O and IrCl3·H2O react with WS42- to give the octahedral complexes M(WS4)33- isolated as their Et4N+ salts. The 183W NMR spectrum of (Et4N)3[Rh(WS4)3] showed a doublet with J(183W,1103Rh) = 4.8 Hz. Thermal gravimetric analyses of [Rh(COD)]2WS4 and (COD)PtWS4 indicate that loss of organic coligands and stoichiometric amounts of sulfur occur at moderate temperatures. The compound [(η5-C5Me5)RhCl]2WS 4·CHCl3 crystallizes in the orthorhombic space group P212121 with a = 13.179 (2) Å, b = 28.725 (7) Å, c = 8.258 (2) Å, V = 3126 (2) Å3, and Z = 4 and was refined to R = 0.052 and Rw = 0.059. The compound [(η3-C3H5)Pd]2WS4 crystallizes in the monoclinic space group P21/c with a = 9.230 (4) Å, b = 9.994 (5) Å, c = 14.780 (7) Å, β = 103.54 (4)°, V= 1325 (1) Å3, and Z = 4 and was refined to R = 0.066 and Rw = 0.079.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry