Electron Paramagnetic Resonance Studies of two Low-Spin Hexacoordinate di(tertiary phosphine) Complexes of Nickel(III)

Single-crystal EPR studies on [Ni(DP)2X2]Y (DP = o-phenylenebis(dimethylphosphine); X- = CI-, Br-; Y- = ClO4- PF-6) doped in the corresponding Co(III) lattices are reported. Principal values of g and the ligand superhyperfine tensors obtained are gxx = 2.1123, gyy = 2.1157, gzz = 2.0089; for 35Cl, Axx = 18.3 ° 1 G, Ayy = 15.3 ° 1 G, Azz - 17.6 ° 1 G and for 31P, Aσ = 13 ° 1 G, Aπ = 5 ° 1 G, Azz = 43.6 ° I G, when X- = CI- and Y- = ClO4- For X- = Br- and = PF6-, the values are gxx = 2.0961, gyy = 2, 1413, gzz = 1.9936; for 81Br, Axx = 61 ° 1 G, Ayy = 26 ° 1 G. Azz = 169 ° 1 G and for 31P, A has a nearly isotropic value of 20 ° 2 G. Comparison is drawn to the previously studied DAS (o-phenyl-enebis(dimethylarsine)) analogue as well as among themselves. © 1979, American Chemical Society. All rights reserved.