**10. References**

594 Advances in Crystallization Processes

the R group from one side and a cluster containing metal-oxygen framework in the other

Application of phosphoryl donor ligands in preparation of oxo-centered clusters, in which their terminal ligands are replaced by phosphorus compounds, may be interesting for consideration. Preparation of single- enantiomer phosphoramidates by using a chiral primary or secondary amine is easy; it may extend the strategies for the synthesis of chiral

Synthesis of phosphoramidate-based hybrid compounds by using polyoxoanions may be valuable for spending the time on its consideration and experiment. Some of the wellknown hybrids contain the molecule-cation components of the type [B—H…B]+, where the B may be a base such as amide. Designing of such molecule-cation pairs with phosphoramidates, [PO—H…OP]+, may extend the experimental data about the 31P-31P

The NMR experiments on phosphoramidate-based compounds may develop the study on coupling constants of phosphorus and the other atoms, such as 2J(31P-127Tl) or 2J(31P-39K). These values may apply to evaluate the strengths of P=O—Tl or P=O—K bonds in their

We wish to develop the spectroscopic features and chemical calculations on phosphorus compounds, preparation of N-deuterated compounds in order to a good assignment of IR and Raman absorption bands, collecting the NMR data such as chemical shifts and short and long-range coupling constants, and finally chemical calculations on hydrogen-bonded

In this chapter, the common methods for the synthesis and crystallization of phosphoramidates, their molecular structural features and the hydrogen-bond patterns and strengths were reviewed; the important structural aspects may be classified as follows:

1. The four different groups linked to the P atom result in a distorted tetrahedral

2. In the C(O)NHP(O) unit, the P=O is a better H-acceptor than the C=O counterpart, moreover, the *anti* orientation of P=O versus C=O is more common than the *gauche* orientation; in acyclic compounds with formula RC(O)NHP(O)[NHR']2, a *gauche* situation has not been reported, so far. In the C(O)NHP(O)[N]2 fragment, the P—N bond of the C(O)NHP(O) moiety is longer than the two other P—N bonds; whereas, in the [C(O)NP(O)[N]2]- fragment, similar P—N bond are shorter than the two others. 3. The nitrogen atom of the P(O)N unit has a sp2 character and virtually doesn't involve in

4. In the C—O—P(=O) fragment, the oxygen of phosphoryl is a better H-acceptor than the

5. In the diazaphosphorinane ring, the P=O bond is placed in an equatorial position. 6. The hydrogen bond in a neutral phosphoramidate is of the type polarization-assisted hydrogen bond; whereas, in the proton-transfer and phosphate compounds two factors

help to strength of hydrogen bond: polarization-assisted and charge-assisted.

side. These acids may develop the extraction process of cations, too.

phosphoramidates, phosphoric acids, nano-phosphates and so on.

coupling constant through the hydrogen-bond.

hydrogen-bond pattern as an H-acceptor.

other oxygen atom; the C—O—P angle is about 120º.

complexes.

molecules in the crystals.

configuration.

**8. Conclusion** 


Phosphoramidates: Molecular Packing and Hydrogen

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results.


**Synthesis and X-Ray Crystal Structure of** 

Yusuke Kataoka3, Yasutaka Kitagawa3 and Mitsutaka Okumura3

Aluminum and its derivatives such as alloys, oxides, organometallics, and inorganic compounds have attracted considerable attention because of their extreme versatility and unique range of properties, including acidity, hardness, and electroconductivity (Cotton & Wilkinson, 1988). Since the properties and activities of an aluminum species are strongly dependent on the structures of the aluminum sites, the syntheses of aluminum compounds with structurally well-defined aluminum sites are considerably significant for the development of novel and efficient aluminum-based materials. However, the use of these well-defined aluminum sites is slightly limited by the conditions resulting from the hydrolysis of the aluminum species by water (Djurdjevic et al., 2000; Baes & Mesmer, 1976;

Polyoxometalates have been of particular interest in the fields of catalytic chemistry, surface science, and materials science because their chemical properties such as redox potentials, acidities, and solubilities in various media can be finely tuned by choosing appropriate constituent elements and countercations (Pope, 1983; Pope & Müller, 1991, 1994). In particular, the coordination of metal ions to the vacant site(s) of lacunary polyoxometalates is one of the most effective techniques used for constructing efficient and well-defined active metal centers. Among various lacunary polyoxometalates, a series of Keggin-type phosphotungstates is one of the most useful types of lacunary polyoxometalates. Fig. 1 shows some examples of lacunary Keggin-type phosphotungstates, i.e., *mono*-lacunary α-Keggin [α-PW11O39]7- (Contant, 1987), *di*-lacunary γ-Keggin [γ-PW10O36]7- (Domaille, 1990; Knoth, 1981), and *tri*-lacunary α-Keggin [A-α-PW9O34]9- (Domaille, 1990) phosphotungstates. Knoth and co-workers first synthesized the Keggin derivative (Bu4N)4(H)ClAlW11PO39 by the reaction of *mono*-lacunary α-Keggin phosphotungstate with AlCl3 in dichloroethane (Knoth et al., 1983). However, only a few aluminum-coordinated polyoxometalates (determined by X-ray crystallographic analysis) have been reported, e.g., a monomeric, *di*-aluminum-substituted γ-Keggin polyoxometalate TBA3H[γ-SiW10O36{Al(OH2)}2(μ-

**1. Introduction** 

Orvig, 1993; Akitt, 1989).

**α-Keggin-Type Aluminum-Substituted** 

Chika Nozaki Kato1, Yuki Makino1, Mikio Yamasaki2,

**Polyoxotungstate** 

*1Shizuoka University 2Rigaku Corporation 3Osaka University* 

*Japan* 

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