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Dioctylphosphinates of the bivalent first-transition-series elements from chromium through zinc have been prepared and characterized. The variety of forms found is discussed. Cobalt(II), iron(II), and manganese(II) yield a form based on octahedral centers which requires multiple sharing of some individual phosphinate oxygens. Chromium(II) and nickel(II) may give similar derivatives. Uranyl phosphinates can be divided into two groups based on solubility. The viscosity and molecular weight data obtained for some of the soluble species indicate that they are polymeric although their solution behavior is not ideal. Infrared and Raman spectra suggest that the uranyl oxygen atoms are not shared in the soluble species and consequently that the bridging is via phosphinate groups. It has proved possible to prepare flexible, strong, crystalline films of the chromium tris(phosphinate) Cr(OP(CH3)(C6H5)O)2(OP(C8H17)2O) reproducibly. (Author), Presented at the National Meeting of the American Chemical Society (164th), Aug 72.

Work was performed toward the synthesis of polymers without carbon-carbon bonds in their backbones in areas ranging from completely inorganic systems to systems based on heterocyclic rings. Technical reports, publications, issued and allowed patents, oral presentations, and daughter contracts stemming from the fundamental program are tabulated, and an abstract is given for each technical report. The most interesting polymers discovered are the poly(metal phosphinates), a family of coordination polymers in which phosphinate anions serve as bridging groups between coordination centers. (Author)

A new form of cobalt(II) dioctylphosphinate (form II) was prepared by the reaction of cobalt(II) chloride with dioctylphosphinic acid in absolute ethanol. Visible and near infrared spectra indicate that form II contains octahedrally coordinated cobalt(II), whereas the previously reported form (form I) contains tetrahedrally coordinated cobalt(II). Form II is irreversibly converted to form I by heating above 68C or by dissolving it in nonpolar solvents. Infrared spectra, X-ray powder patterns, and DSC thermograms for both forms are presented and compared. This appears to be the first example of a poly(metal phosphinate) which exists both in four- and six-coordinate forms. (Author)

General procedures avoiding the use of chromium(II) intermediates are presented for the synthesis of two types of chromium(III) bis(phosphinate) polymers, (Cr(H2O)(OH)(OPRR'O)2)x and (Cr(OH)(OPRR'O2)x. (Author)