Platinum Metal Thioether Macrocyclic Complexes: Synthesis, Electrochemistry, and Single-crystal X-Ray Structures of cis-2>PF6 and trans-3>PF6 (L2 = 1,4,8,11-tetrathiacyclotetradecane, L3 = 1,5,9,13-tetrathiacyclohexadecane)

Article abstract of DOI:10.1039/DT9890001675

Reaction of RhCl3 with 1 mol equivalent of L<1,4,7,10-tetrathiacyclododecane (L¹), 1,4,8,11-tetrathiacyclotetradecane (L²), and 1,5,9,13-tetrathiacyclohexadecane (L³) in refluxing MeOH affords the rhodium(III) complex cations (1+).The complex cis-2>PF6 crystallises in the monoclinic space group C2/c, with a = 10.746(8), b = 11.298(5), c = 15.708(8) Angstroem, β = 92.00(5) degree, and Z = 4.A single-crystal X-ray structure shows the cation sitting on a crystallographically imposed C₂ axis with octahedral Rh(III) bound to two mutually cis chloro ions .The tetrathia macrocycle adopts a folded conformation with S(1) and S(8) trans to chloride, Rh-S(1) 2.287 0(12) and Rh-S(4) 2.3275(12) Angstroem.The trans isomer has not been detected spectroscopically in reactions of Rh(III) with L¹ and L²; the tendency of these ligands to coordinate to second- and third-row transition-metal ions to form cis complexes is ascribed to the large radii of these metal ions relative to the cavity size of the 12- and 14-membraned rings.This is confirmed by structural analysis of 3>PF6 which shows mutually trans chloro ligands, Rh-Cl 2.3391(22) Angstroem.The complex trans-3>PF6 crystallises in the monoclinic space group C2/c, with a = 11.9507(20), b = 11.1055(15), c = 16.2067(18) Angstroem, β = 95.197(21) deg., and Z = 4.The single-crystal X-ray structure shows Rh(III) on an inversion centre with the six-membered chelate rings of the macrocycle adopting alternate chair and twist-boat conformations, Rh-S(1) 2.3483(25) and Rh-S(5) 2.3483(27) Angstroem.

Full text of DOI:10.1039/DT9890001675

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