31P-NMR and X-Ray Studies of the Complexes [HgX2 (1)]. (1=2, 11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene,X=Cl,I) |
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Authors: | Roland W. Kunz Paul S. Pregosin Mercedes Camalli Francesco Caruso Luigi Zambonelli |
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Abstract: | 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 . |
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