Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

Abstract

The reactions of Hg2(AsF6)2 with P(CF3)3, PF3, PCl3, P(CF3)Ph2, PClPh2, PPh3, P(OMe)3, AsPh3, SbPh3, SPPh3, SP(p-C6H4F)3, and SePPh3 in liquid sulfur dioxide have been studied. The last five ligands form insoluble 1:1 complexes, Hg2(AsF6)2•L, if L:Hg22+ ≤ 1, but disproportionation of the mercurous ion occurs if L:Hg22+ > 1; the 1:1 mercurous complexes have been characterized by analysis and vibrational spectroscopy. There is no evidence for complexation of P(CF3)3. PPh3 and P(OMe)3 cause disproportionation of the mercurous ion under all conditions; Hg(PPh3)22+ and Hg(P(OMe)3)22+ have been characterized by 13C and 1H nmr respectively. When P(CF3)Ph2:Hg22+ ≤ 1 soluble Hg2(P(CF3)Ph2)2+ is formed; the 19F and 13C nmr spectra of this complex are reported, as are those of Hg(P(CF3)Ph2)22+. In the system PF3–Hg2(AsF6)2–SO2 no disproportionation occurs; 19F nmr provides evidence that Hg2PF32+ and, probably, Hg2(PF3)22+ are formed. 1J(P–F) in mercurous and silver(I) complexes of PF3 is of unusually large magnitude. The 13C nmr spectra of Hg(PPh3)22+, Hg2(P(CF3)PPh2)2+, and Hg(P(CF3)Ph2)22+, are consistent with the occurrence of little metal-to-phosphorus back-bonding in these phosphine complexes. The relationship between the net electron donating ability of a phosphine and the nature of its interaction with the mercurous ion is discussed.

Syntheses and Vibrational and13C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)2][Sb2F11]2) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg2(CO)2][Sb2F11]2) and the Molecular Structure of [Hg(CO)2][Sb2F11]2

“…A precedent for [Hg 2 (CO) 2 ] 2+ may be found in cations of the type [Hg 2 (PF 3 ) n ] 2+ , n = 1 or 2, formed by the addition of PF 3 to Hg 2 [AsF 6 ] 2 in SO 2 and detected by 19 F and 31 P NMR and Raman spectroscopy at 0 °C . The cations appear to decompose quickly at room temperature to PF 5 and AsF 3 .…”

Nuclear magnetic resonance studies of the solvation of phosphorus(V) selenides, 1,2-bis(diphenylphosphino)ethane, and tris(dimethylamino)phosphine telluride by sulfur dioxide

“…The stability of the diphosphine adduct is only a little less than those of the diphosphine diselenides, and like the selenides the diphosphine is apparently totally complexed in liquid SO,. Earlier, it has been suggested on the basis of 13C nmr data that PPh, is totally complexed in SO, (1). The earlier data for the system PPh,-SO,-CS, can be used to estimate that K, for Ph,P.SO, is ca.…”

One-Pot Synthesis of Aryl Selenonic Acids and Some Unexpected Byproducts

“…1 H, 13 C, 19 F, and 77 Se NMR spectra were recorded in D 2 O or CDCl 3 at 400, 101, 377, and 76 MHz, respectively. External references of C 6 F 6 in C 6 D 6 (δ −164.9 ppm relative to CFCl 3 ) or PhSeSePh (δ 463 relative to Me 2 Se), respectively, were used. 13 C and 19 F NMR spectra were recorded with broadband proton decoupling.…”