31P‐NMR and X‐Ray Studies of the Complexes [HgX2 (1)]. (1=2, 11‐bis (diphenylphosphinomethyl)benzo [c]phenanthrene, X=Cl, I)

The 31P{1H}‐NMR characteristics of the complexes [HgX2(1)] and [HgX2‐(PPh2Bz)2] (X = NO3, Cl, Br, I, SCN, CN) and the solid state structures of the complexes [HgCl2(1)] and [HgI2(1)] (1 = 2,11‐bis (diphenylphosphinomethyl)benzo‐[c]phenanthrene) have been determined. The 1J(199Hg, 31P) values increase in the order CN < I < SCN < Br < Cl < NO3. The two molecular structures show a distorted tetrahedral geometry about mercury. Pertinent bond lengths and bond angles from the X‐ray analysis are as follows: HgP = 2.485(7) Å and 2.509 (8) Å, HgCl = 2.525 (8) Å and 2.505 (10) Å, PHgP = 125.6(3)°, ClHgCl = 97.0(3)° for [HgCl2(1)] and HgP = 2.491 (10) Å and 2.500(11) Å, HgI = 2.858(5) Å and 2.832(3) Å, PHgP = 146.0(4)°, IHgI = 116.9(1)° for [HgI2(1)]. The equation, derived previously, relating 1J(199Hg, 31P) and the angles PHgP and XHgX is shown to be valid for 1.