Dithioacid complexes reactions

The reaction of (CH3XCF3)3PN(CH3)2 with CS2 proceeds with CS2 insertion into the P-N bond and formation of the (CH3XCF3)3F(Me2Dtc) compound (S90). Very little is known about the chemistry of the xanthate or dithioacid complexes of the Group V elements. The P(EtXant)3 has been reported (410). The IR spectrum of this molecule and those of the corresponding As(III) and Sb(III) compounds show a monotonic decrease of the C—O vibration around 1200 cm 1 (by 7 cm-1 intervals) from P to Bi (635). 

Numerous complexes of nickel(II) with phosphorodithioate ligands (also called dithio-phosphates 280 R — R" = 0-alkyl, O-aryl) and dithiophosphinates (280 R = R" = alkyl, aryl) have been reported to date. A few dithiophosphonato complexes (280 R = alkyl, R" = O-alkyl) were also reported. The bis(dialkyldithiophosphato)nickel(II) complexes were obtained as purple diamagnetic compounds by means of the direct synthesis between the appropriate dithioacid (RO)2P(S)SH and a nickel(II) salt, often the acetate hydrate. The dithioacid can be conveniently prepared in situ, by reacting P4Si0 with the appropriate alcohol which sometimes acts by itself as reaction medium. Structural properties of selected nickel(II) complexes are reported in Table 90. 

Very recently the synthesis of the hitherto unknown aromatic xanthate ligands was reported by Fackler et al., who also determined several crystal structures of arylxanthate complexes (117, 238). The synthesis and reactions of air-stable piperidinium salts of aliphatic dithioacids have been reported (377). 

Reaction of [MoX2(CO)3(NCMe)2] with two equivalents of dithioacid ligands affords complexes of the type [Mo(CO) (S2CX)2], for example, [Mo(CO)3 S2P(OEt)2 2], which reacted with tertiary phosphines forming [Mo(CO)2 (PPh3) S2P(OEt)2 2] and [Mo(CO)(diphos) S2P(OEt)2 2]. Similar species containing S2CPCy3 were also prepared. 

The reaction of tetraphosphorus decasulfide with primary amines (1 12 M ratio) gives fhiophosphoryltriamides, SP(NHR2)3 with a 1 8 ratio, the product is a dithiophos-phoric acid diamide (RNH)2P(S)(SH) (Scheme 23). The dithioacid diamides form metal complexes, for example, Ni[S2P(NHPh)2]2. ... 

---