REACTIVITY THE TRIETHYLPHOSPHINECARBON DISULFIDE ADDUCT Et3PCS2 TOWARD IRON(II) CATIONS IN THE PRESENCE OF THE BIS(TERTIARY PHOSPHINES), depe, AND diphos. X-RAY CRYSTAL STRUCTURES OF THE COMPLEXES (BPh4)2 AND (BPh4)

Article abstract of DOI:10.1016/S0022-328X(00)82703-5

Reaction of the triethylphosphinecarbon disulfide adduct Et3PCS2 with iron(II) aquocations in the presence of the bis(tertiary phosphines) depe or diphos, and NaBPh4 has given the monomeric complexes <(depe)2Fe(S2CPEt3)>(BPh4)2, 1, and <(diphos)Fe(S2CPEt3)2>(BPh4)2 * 0.5(CH3)2CO, 3 (depe = 1,2-bis(diethylphoshino)ethane; diphos = 1,2-bis(diphenylphosphino)ethane).Compound 1 undergoes nucleophilic attack by hydride ion on the coordinated Et3PCS2 ligand to give the dithioformato derivative <(depe)2Fe(S2CH)>(BPh4), 2.The structures of compounds 1 and 2 have been determined from counter diffraction X-ray data.Crystal data for 1 are: triclinic, space group P<*>, a 18.583(8), b 14.836(7), c 14.019(7) Angstroem, α 94.38(4), β 102.56(4), γ 103.34(4) deg, Z = 2, R = 0.080.Crystal data for 2 are: monoclinic, space group P2₁/a, a 28.912(10), b 11.949(6), c 13.386(7) Angstroem, β 94.35(5) deg, Z = 4, R = 0.076.In both structures the iron atom displays a distorted octahedral geometry, being linked to the phosphorus atoms of two depe molecules and to the two sulfur stoms of the zwitterion in compound 1 or of the dithioformato group in compound 2.