Zr-COOH

Zr-COOH-OH was prepared by predpitating with an aqueous sdution... 

Zr-COOH-H was prepared by precipitating 7i with an aqueous scJution of a 2 1 mdar ratio of phosphorous add and 2-carboxyethylphosphonic add. The powdCT XRD pattern of this material contains reflectiais frcMn three distinct phases. The interlayer spacings d these phases are 19.6,12.7 and 6.5 A. The 12.7 A phase likely contains mostly phosphonate pendant groups, while the 6.5 A phase probably... 

The IR spectrum erf" Zr-COOH-H looks like that of Zr(03FCH2CH2COOH)2 with a superimposed P-H stretch at 2473 cm"l. The 1703 emr C=0 stretch of Zr COOH-H suggests a similarity between these carboxylic add groups and those found both in Zr-COOH-OH and Zr(03PCH2CH2C0aT)2. The CP MAS NMR... 

Heating Zr-COOH-OH and Zr-COOH-H to 170 C undo vacuum to drive off interstitial wat pdex to treatment with refluxing SOQ2 increased the yield dboth acyl chlorides, but still did not result in full ccaiversicxiddther. The IR spectrum d the reaction paxxluct frexn dehydrated Zr-COOH-OH (Hgurc 4a) exhibited distinct... 

Figure 4. IR spectra of products from reaction of S(X l2 with dehydrated Zr-COOH-OH (top) and non-dehydrated Zr-COOH-H (bottom).

When Zr-COOH-OH was treated with hexylamine directly, the product showed four orders of ((X)/) reflections in the powder XRD pattern from a 26.2 A phase. This compares to a interlayer spacing of 28.7 A for the hexylammonium intercalate of Zr(03PCH2CH2C00H)2. Curiously, both the IR and l C NMR spectra of this product suggest that a small amount amide was formed in addition to the expected hexylammonium product. 

When the partially converted acyl chloride derivative of Zr-COOH-H was contacted with hexyl alcohol, a phase of interlayer spacing 28.5 A was formed— an increase of 8.9 A over the 19.6 A separation of the host. This can be compared to a 12.7 A increase in interlayer spacing upon conversion of Zr(03PCH2CH2C00H)2 to Zr(03PCH2CH2C00C6Hi3)2. The 12.7 A phase of Zr-COOH-H appears to have... 

Synthesis of Zr(03PCH2CH2COCl)i.5(O OH)o.5. Zr-COOH-OH (0.5 g) was placed in a flask and dehydrated by healing to 170 C under vacuum for 3 hours. The flask was then coded to 0 C under nitrogen and 15 ml SOCI2 (previously cooled to 0°Q was added to the flask. The tempaatured the mixture was raised to 90 C and held there for 16 days under an nitrpgaiatmos iae. TheSOQ2 was removed and the product dried under vacuum. 

Synthesis of Zr(03PCH2CH2COCi)i.25(03PH)o.75- Zr-COOH-H (1.2 g) was added to 25 ml SOCI2 previously coded to 0 C under a nitrogen atmosphere. The mixture was stim 2 weete at 90 C under a nitrpgai atmoi ere. The SOQ2 was removed and the xoduct dried under vacuum. 

Figure 3. Schanadc drawings of (a) Zr(03PCH2CH2CC)0t j (03P0H)q 0.5H20 and (b) Zi<03Pa a cooH)j 25(O3PH) 75-05 a...

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