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

The 31 P{ 1 H}‐NMR characteristics of the complexes [HgX 2 ( 1 )] and [HgX 2 ‐(PPh 2 Bz) 2 ] (X = NO 3 , Cl, Br, I, SCN, CN) and the solid state structures of the complexes [HgCl 2 ( 1 )] and [HgI 2 ( 1 )] ( 1 = 2,11‐bis (diphenylphosphinomethyl)benzo‐[ c ]phenanthrene) have been determined. The 1 J ( 199 Hg, 31 P) values increase in the order CN < I < SCN < Br < Cl < NO 3 . 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: HgP = 2.485(7) Å and 2.509 (8) Å, HgCl = 2.525 (8) Å and 2.505 (10) Å, PHgP = 125.6(3)°, ClHgCl = 97.0(3)° for [HgCl 2 ( 1 )] and HgP = 2.491 (10) Å and 2.500(11) Å, HgI = 2.858(5) Å and 2.832(3) Å, PHgP = 146.0(4)°, IHgI = 116.9(1)° for [HgI 2 ( 1 )]. The equation, derived previously, relating 1 J ( 199 Hg, 31 P) and the angles PHgP and XHgX is shown to be valid for 1 .