No abstract

No abstract

The known mixed halide-phosphine (or -arsine) TBP complexes of nickel(II) are blue, green, or purple. The corresponding SPY complexes are red, brown, or purple, and if the number and kind of ligands are the same in the two geometries, as in those discussed here, the lowest energy ligand-field band occurs at lower energy in the case of the TBP. When we go to the mixed cyanidearsine, however, the result is that the lowest energy absorption maximum is found in the SPY spectrum.The lowest energy band in the SPY complex is of relatively low intensity (for [Ni(diars)2CN]+, e is 420 in 2-methyl-TBP-methanol at 300°K). If we compare the most intense ligand-field bands for the two compounds, we find that for both cyanides and halides, the intense absorption at lower energy is found in the TBP.(2) This paper is based in part on a dissertation submitted by L. B. Handy to the Graduate School of the University of Wisconsin in partial fulfillment of the requirements for the Ph.D. degree, Aug 1968.

The triplet is assigned to the CF2 group and the singlet to the CF3 group. Apparently the CF2 group and the CF3 group do not couple. The area ratio due to the SF2, CFS, and CF2 group fluorine atom resonances is 2.0: 5.9:4.1, respectively. The 19F n.m.r.spectra of the saturated products, CF3NFSF5 and C2FbNFSFb, are more complex. No attempt was made to analyze the bands attributable to the SF5 groups which have AB4 patterns. The major bands of these groups are centered at -58.2 and -60.5 for CF3NFSFB and C2FBNFSFB, respectively. The two other bands in the spectrum of CF3NFSFb are found at 48.2 and 70.3 and are assigned to the NF and CF3 groups. The area ratio for SFB: NF:CF3, 5.1:1.0:3.1, respectively, is consistent with the assignments. In the spectrum of C2FbNFSFb the broad band at 49.4 is assigned to the NF fluorine while the doublet (Jff = 10 c.p.s.) at 81.7 and the band at 110.1 are assigned to the CF3 and CF2 groups, respectively. The band at 81.7 coalesced into a singlet when the band at 49.4 was (Z) Modification No. 15.

No abstract