Arsenic chloride complex anions

The green phosphoric acid from a phosphoric acid plant (PAP) contains 25-30% H3PO4. The acid is heavily entrained with impurity cations, among which arsenic, cadmium, and uranium are the most toxic. In addition, anions, like chloride, fluoride, and sulfate must be considered. Selective extraction of phosphoric acid [18] as an adduct complex with TBP according to the block diagram in Fig. 14.12 has been used to produce acid of food grade. 

The formation of the heterocycle 1 from the xylylene-bis-phosphonium salt 2 and PCI3 proceeds via a detectable intermediate 3 in a cascade of condensation reactions that is terminated by spontaneous heterolysis of the last remaining P-Cl bond in a cyclic bis-ylide-substituted chlorophosphine formed (Scheme 1) [15]. The reaction scheme is applicable to an arsenic analogue of 1 [15] and to bis-phosphonio-benzophospholides with different triaryl-, aryl-alkyl- and aryl-vinyl-phosphonio groups [16, 18, 19], but failed for trialkylphosphonio-substituted cations here, insufficient acidity prohibited obviously quantitative deprotonation of the phosphonium salts, and only mixtures of products with unreacted starting materials were obtained [19]. The cations were isolated as chloride or bromide salts, but conversion of the anions by complexation with Lewis-acids or metathesis was easily feasible [16, 18, 19] and even salts with organometallic anions ([Co(CO)4] , [CpM(CO)3] (M=Mo, W) were accessible [20]. 

The crystalline addition complex formed between phosphorus trichloride and tetraethylammo-nium chloride is quite unusual, and is correctly formulated as Et4N+ PCI4 [42], Unlike the tetrahedral PCI4 cation, the PCI4 anion adopts a distorted trigonal bipyramidal configuration in which one equatorial arm is believed to be occupied by a lone pair of electrons (4.298). In this instance, there is a resemblance to the stereochemistry of arsenic and antimony (Chapter 3.2). 

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