Phosphides actinide

The phosphido complex, Th(PPP)4 [143329-04-0], where PPP = P(CH2CH2P(CH2)2)2) has been prepared and fully characterized (35) and represents the first actinide complex containing exclusively metal—phosphoms bonds. The x-ray stmctural analysis indicated 3-3-electron donor phosphides and 1-1-electron phosphide, suggesting that the complex is formally 22-electron. Similar to the amido system, this phosphido compound is also reactive toward insertion reactions, especially with CO, which undergoes a double insertion (35,36). 

In the review by Kanatzidis et al. (2005), the preparation by the tin-flux method is mentioned also for several ternary phosphides and polyphosphides of rare-earth and transition metals. Typically the components (R metal, T metal, P and Sn in an atomic ratio of about 1 4 20 50) in sealed silica tubes were slowly heated, to avoid violent reactions, up to 800°C, annealed at that temperature for 1 week and slowly (2 K/h) cooled to ambient temperature. The tin-rich matrix was dissolved in diluted hydrochloric acid. The authors described the preparation of compounds corresponding for instance to the formula MeT4P12 (Me = heavy rare-earth metals and Th and U, T = Fe, Ru, etc.) and to the series of phases MeT2P2 (Me is a lanthanide or an actinide and T a late transition metal) having a structure related to the BaAl4 or ThCr2Si2 types. 

Handwerk, J. H., Kroger, O. L., Phosphides, sulfides, and other actinide fuel compounds as possible ceramic fuel material, Nucl. Eng. Des., 17, (1971), 397-408. Cited on page 306. 

Fig. 21. Logarithm of upstroke-transition pressure versus cation/anion radius ratio for the B1 to B2 transition in lanthanide and actinide compounds. Trivalent ionic radii are used for all cations. Some transitions to other high-pressure structures are included for comparison and have been marked as such in the graphs, (a) Mono-pnictides with As, Sb, and Bi. The isolated data for the phosphides CeP and ThP are not included. No mononitrides have been observed to transform to the B2 type under pressure, (b) Mono-chalcogenides with S, Se, and Te. The EuO transition is outside the graph.

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