Tetrathiometalate Complexes of Rhodium, Iridium, Palladium, and Platinum. Structures of [(C5Me5)RhCl]2WS4 and [(C3H5)Pd]2WS4

Synthetic routes to tetrathiometalate complexes of rhodium, iridium, palladium, and platinum are described. Acetonitrile solutions of WS/sub 4//sup 2 -/ reacted with (Rh(diene)Cl)/sub 2/ (where diene = 1,5-cyclooctadiene (COD) or norbornadiene (NBD)), (Ir(COD)Cl)/sub 2/, ((/eta//sup 5/-C/sub 5/Me/sub 5/)RhCl/sub 2/)/sub 2/, and (Pd(allyl)Cl)/sub 2/ to give good yields of ..mu..-WS/sub 4/ complexes (Rh(diene))/sub 2/WS/sub 4/, (Ir(COD))/sub 2/WS/sub 4/, ((/eta//sup 5/-C/sub 5/Me/sub 5/)RhCl)/sub 2/WS/sub 4/, and ((allyl)Pd)/sub 2/, respectively. (COD)PtCl/sub 2/ reacted with MS/sub 4//sup 2 -/ to give (COD)PtMS/sub 4/, M = Mo, W. The later complexes react further with PPh/sub 3/ or WS/sub 4//sup 2 -/ to give (PPh/sub 3/)/sub 2/PtMS/sub 4/ and Pt(WS/sub 4/)/sub 2//sup 2 -/, respectively. (Rh(COD))/sub 2/WS/sub 4/ reacted with t-BuNC to give (Rh(t-BuNC)/sub 2/)/sub 2/WS/sub 4/. RhCl/sub 3/ x 3H/sub 2/O react with WS/sub 4//sup 2 -/ to give the octahedral complexes M(WS/sub 4/)/sub 3//sup 3 -/ isolated as their Et/sub 4/N/sup =/ salts. The /sup 183/W NMR spectrum of (Et/sub 4/N)/sub 3/(Rh(WS/sub 4/)/sub 3/) showed a doublet with J(/sup 183/W,/sup 103/Rh) = 4.8 Hz. Thermal gravimetric analyses of (Rh(COD))/sub w/WS/sub 4/ and (COD)PtWS/sub 4/ indicate that loss of organic coligands and stoichiometric amounts of sulfur occur at moderate temperatures. The compound ((/eta//sup 5/-C/sub 5/Me/submore » 5/)RhCl)/sub 2/WS/sub 4/ x CHCl/sub 3/ crystallizes in the orthorhombic space group P2/sub 1/2/sub 1/2/sub 1/ with a = 13.179 (2) /angstrom/, b = 28.725 (7) /angstrom/, c = 8.258 (2) /angstrom/, V = 3126 (2) /angstrom//sup 3/, and Z = 4 and was refined to R = 0.052 and R/sub w/ = 0.059.« less