Phosphides crystal structures

Until very recently, the only example of a quasi-3-coordinate aluminum phosphide was (Me3SiCH2)2AlPPh2,76 which was reported to exist in solution as a monomer-dimer equilibrium. However, a crystal structure of... 

The thermal and photochemical reactions of Ir111 complexes (438) and (439), respectively, yield the same product species (440), R2 = Ph2, Me2, HPh.692 Kinetic studies indicate that the reaction involves the direct reductive transfer of the methyl to the phosphide via a three-centered transition state. The crystal structures of (438) and (439) (R2 = Ph2) are reported. 

Dimeric zinc complexes of tertiary phosphines, [Zn(PR3)I2]2, are also formed from zinc powder and R3PI2, (R = Me, Et, n-Pr, ra-Bu). The crystal structure of the ethyl derivative demonstrates the dimeric nature of the complexes.295 Metallation of diphenylphosphine with ZnEt2 results in a trimeric species with a Zn3P3 core and bridging diphenyl phosphide ligands. Two protic (HPPh2)... 

Phosphides. The crystal structure of MogPj has been shown to involve trigonal prisms of molybdenum atoms each enclosing a central phosphorus atom. M0P4 has been prepared by reaction of the elements at 15—65 kbar and shown to be isostructural with CrP, and therefore to involve the metal atom surrounded by six phosphorus atoms in a distorted octahedral manner. ... 

The compounds with larger negative ions, like sulphides, selenides and phosphides, in many respect resemble the interstitial compounds. Like the latter, they often show metallic properties and have variable compositions, but their crystal structures are of quite a different type. 

Lithium t-butyldimethylsilyl(2,4,6-tri-t-butylphenyl)phosphide (lib) was allowed to react with benzoyl chloride to give (E)- and (Z)-Mes P=C(OSiMe2Bu-t)Ph (equation 81)3. The E- and Z derivatives were separated and the configuration of (Z)-Mes P=C(OSiMe2Bu-t)Ph was unambiguously determined by the X-ray crystal structure analysis94. Irradiation of ( )-Mes P=C(OSiMe2Bu-t)Ph in benzene resulted in... 

Boron phosphide occurs in two forms, one of which, cubic BP, has a diamondlike structure analogous to cubic boron nitride (see above). The other variety, Bi2PL8, has a partially disordered crystal structure that contains icosahedral Bi2 units, as found in many metal borides (Section 5-3). Cubic BP is extremely inert, resisting attack by boiling concentrated acids or bases, is not oxidized in air below... 

Figure 20 Crystal structures of various ternary and quaternary phosphide oxides of the alkaline earth, rare earth, and actinoid metals. Alkaline earth (rare earth, actinoid), transition metal, phosphorus, and oxygen atoms are drawn as large light grey, medium grey, filled, and open circles, respectively. Some relevant coordination polyhedra around the oxygen atoms and the transition metal-phosphorus bonds are emphasized...

The crystal chemistry of the phosphide oxides discussed above is closely related to the structural slabs of the well-known BaZn2P2 type (isolated /BaAU type (P2 pairs) and related compounds. This is different for the phosphide halide structures. Some relevant structures of the phosphide halides are presented in Figure 21 and a list is given in Table 9. These structures contain isolated phosphorus atoms, P2 pairs, or one-dimensional spirals like in the structure of elemental selenium. 

With A = Rb and Cs, compounds of the type A2[PH] can be prepared containing an isolated hydrogenphosphide anion [PH] , which could also be named for example, as dicesiumphosphanide(l), when starting from phosphane(3). The orientation of the PH unit could not be determined by X-ray analysis, but its existence has been proven by solid-state H-NMR. The metal phosphide Ti3P forms hydrides or deuterides up to a maximum content of 2.6 H (D). The exact crystal structure depends on the H (D) content and the temperature. We note, that exact reliable studies of compounds M/P/H are very rare. 

Figure 24 Magnetic ordering temperatures of uranium nickel phosphides with crystal structures belonging to two different structural families (from Ebel et al )...

This reaction also takes place for the chelated derivative, [(N3N)Ta(PHR)2] [N3N = (Me3SiNCH2CH2)3N and R = Ph, Cy, r-Bu] prepared from the lithiated phosphides in Et20 at 25°C . The resulting phosphinidenes are isolated as pale yellow powders in 87% yield. The crystal structure for R = Cy reveals a Ta=P bond length of 2.145(7) A. 

There are many compounds in which As and Sb form tetrahedral bonds (valence group 8) as, for example, GaAs, GaSb, InAs, and InSb which, like the corresponding phosphides, crystallize with the zinc-blende structure. Tetrahedral bonds are formed by As in the ASO4 ion in orthoarsenates (and arsine oxides) but note the quite different behaviour of Sb in its oxy-compounds (see later). 

Tin Phosphides, Several stoichiometries reported Mellor s voI. VIII, 847-849 (1931), Crystal structure of Sn,P2 and discussion of other phases Olofsson, Acta Chem. Scand. 21, 1659 (1967) 24, 1153 (1970). 

Table V-31 Stoichiometries and crystal structure parameters for zirconium phosphide compounds...

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