Jin-Can Yang, J. Drake, S. Hernández-Ortega
Sep 30, 1997
Citations
0
Influential Citations
24
Citations
Journal
Polyhedron
Abstract
A new method of synthesis, i.e. the reaction between Li[HN(S)PPh 2 ] and Ph 2 P(O)Cl in a diethyl ether/ n -hexane mixture, was used for the preparation of tetraphenylmonothioimidodiphosphinic acid. Its sodium salt was obtained by reacting the free acid with NaH in THF. The solid state structures of both compounds were determined by X-ray crystallography. (OPPh 2 )(SPPh 2 )NH ( 1 ) contains two independent molecules in the unit cell. Both molecules exhibit an anti conformation of the chalcogen atoms in the OPNPS system. In the crystal the molecules of 1 are associated into polymeric chains through hydrogen bonds involving only the oxygen atoms of each molecule [av. (N )H/3.O 2.09A]. the sodium salt of this acid can be considered to be built up of centrosymmetric dimers [Na(OPPh 2 )(SPPh 2 )N · 2THF] 2 ( 2 ). The O atom of the ligand unit acts as a bridging between the two Na atoms of the dimer [Na(1) O(1) 2.245(9), Na(1) O(1)′ 2.396(9)A]. In addition Na(1) is also coordinated by the S(1)′ atom [Na(1) S(1)′ 2.975(6)A] and the oxygen atoms of the two THF molecules [Na(1) O(2) 2.37(1), Na(1) O(3) 2.35(1)A]. This results in a trigonal bipyramidal geometry around sodium atoms [O(1)′ and O(3) in axial positions for Na(1), O(3) Na(1) O(1)′ 171.5(4)°], and a tricyclic system with a central planar four-membered Na 2 O 2 ring.