Phosphorus phosphorus compounds with the coordination number 4

Complexes of hexamethylphosphoramide with mercury(II) salts

α-Tetraphosphor-trithio-dijodid 1 reagiert mit Metallcarbonylen M(CO)n (M = Ni, Fe) sowie mit gemischten Carbonyl-Verbindungen MLx(CO)y (M = Cr, Mo, W; L = THF, C7H8, CH3CN, C6H5CH3) unter Bildung von Komplexen des Types [M(α-P4S3J2)m(CO)n−m (M = 1–3). Mit (CO)3]2, wahrend in Tetrahydrofuran unter Valenzdisproportionierung der ionogene Komplex [Co(α-P4S3J2)2(CO)3]⊕[Co(CO)4]⊖ gebildet wird. Verbruckte Komplexe [(CO)n−1M(α-P4S3J2)M(CO)n−1] konnten nicht erhalten werden. 1 fungiert demnach ausschlieslich als 1-zahniger Ligand. Die dargestellten Komplexe besitzen daher trotz ihrer Schwerloslichkeit eindeutig molekularen Aufbau und keine polymere Struktur.



Contributions to the Chemistry of Phosphorus. 63. α-Tetraphosphorus-trithio-diiodide as a New Ligand in Carbonyl Complexes



α-Tetraphosphor-trithio-dijodid 1 reacts with metal carbonyles M(CO)n (M = Ni, Fe) and with mixed carbonyl compounds MLx(CO)y (M = Cr, Mo, W; L = THF, C7H8, CH3CN, C6H5CH3) to give complexes of the type [M(α-P4S3J2)m(CO)n−m] (M = 1–3). With [Co(CO)4]2 in carbons disulfide or benzene results the substitution product [Co(α-P4S3J2)(CO)3]2, whereas in tetrahydrofurance the ionice complexe [Co(α-P4S3J2)2(CO)3]⊕[Co(CO)4]⊖ is for, ed via valence disproportionation. Bridged complexes [(CO)n−1M(α-P4S3J2)M(CO)n−1] could not be obtained. Therefore, 1 acts exclusively as monodentate ligand, and the prepared complexes possess unambiguouslya molecular and not a polymeric structure, in spite of their low solubility.

Beiträge zur Chemie des Phosphors, 63. α-Tetraphosphor-trithio-dijodid als neuer Ligand in Carbonyl-Komplexen†

Phosphorus triiodide has been prepared in high yields by the high-temperature reaction of metal iodide, metal phosphate, and silicon dioxide. Mixtures with europium, lanthanum, and strontium as the metallic element react under vacuum a t 800-1000 OC to produce large quantities of hexagonal (a = 7.133 (2), c = 7.414 (2) A) phosphorus triiodide and smaller quantities of diphosphorus tetraiodide and a polymorphic form of phosphorus. Products of the europium system have been characterized and include europium(I1) silicate, EuSi03, and europium(I1) tetraeuropium(II1) oxide trisilicate, EusO(Si04)3. Europium(I1) diiodide, EuI2, europium(I1) diiodide hydrate, EuIpH20, and silicon tetraiodide have also been identified as side products. X-ray data are reported for the products and the mass spectrum of PI3 has been obtained. The preparative reactions are presented, and thermodynamic calculations for the processes are described.

Reactions of strontium, lanthanum, and europium iodides. Direct preparation of phosphorus triiodide from phosphates

Pyrophosphate complexes of copper(II)

Bei Anwendung einer stochiometrisch kontrollierten Halogenierung von (I) mit einer Reihe von Reagenzien werden teilweise B-halogenierte Derivate von (I) dargestellt.

Phosphorus phosphorus compounds with the coordination number 4

References

Complexes of hexamethylphosphoramide with mercury(II) salts

Beiträge zur Chemie des Phosphors, 63. α-Tetraphosphor-trithio-dijodid als neuer Ligand in Carbonyl-Komplexen†

Reactions of strontium, lanthanum, and europium iodides. Direct preparation of phosphorus triiodide from phosphates

Pyrophosphate complexes of copper(II)

Synthesis and characterization of some partially B-halogenated 1,2,3,4,5,6-hexahydrocyclotriboraphosphanes

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