The macrocyclic polyether benzo-15-crown-5 reacts with the hydrated lanthanide(III) nitrates in acetone solution to form complexes of the type Ln(N03)3-Ci4H2oOs (Ln = La, Ce, Pr, Nd, and Sm) with the lighter (i.e., larger) lanthanides and of the type Ln(N03)3 • 4 2 05• 3H20 -(

Two isomers of the linear tetratertiary phosphine (C6H5)2ΡCH2CH2Ρ(C6H5)CH2H2Ρ(C6H5)CH2CH2Ρ- (C6H5)2 with widely differing solubilities and melting points can be obtained from the base-catalyzed addition of C6H5P(H)CH2CH2P(H)C6H5 to two equivalents of diphenylvinylphosphine; these appear to be the dl and meso diastereoisomers arising from the two equivalent asymmetric phosphorus atoms.

Sodium N,N-diethyldithiocarbamate reacts smoothly with rnethylene chloride (even in the presence of various transition metal ions) to give the dithiocarbamate ester Et2NC(S)SCH2S(S)CNEtz in very high yield. With chloroform and acetonitrile, proton abstraction occurs followed by partial decomposition of the N,N-diethyldithiocarbamic acid so formed to give diethylammonium N,N-diethyldithiocarbamate.Canadian Journal of Chemistry, 48,3827 (1970) Although there is a very considerable literature on the synthesis of metal N,N-dialkyldithiocarbamate complexes in aqueous solutions (I), it is only recently that reactions between metal halides and sodium N,N-diethyldithiocarbamate (Nadtc) have been examined under anhydrous conditions (2). In almost all cases, the metal-dtc complex is the major product although in certain reactions aimed at the synthesis of pentakis-(N,Ndimethyldithiocarbamato)Nb(V), an organic product, tetramethylthiuram disulfide [(Me2-NCS,),] has been isolated (3). It appears that the metal is reduced to Nb(1V) and the tetramethylthiuram disulfide is produced via the radical Me2NCS2'. In no case, however, has there been mention of the possibility of a reaction between Nadtc and the anhydrous organic solvent.As a continuation of our work on anhydrous metal halide -dtc systems (4), we have carried out reactions between sodium N,N-diethyldithiocarbamate and halides of Nb(V), Ta(V), Pa(V), and Mo and W (in various oxidation states) in several organic solvents under anhydrous and inert atmosphere conditions. These reactions produce not only the expected metal halide -dtc complexes (to be reported in separate papers) but also totally unexpected organic products formed by reactions of the Nadtc with the solvents. Indeed, in some reactions, the organic products are formed in very high yield to the almost complete exclusion of the metal halide -dtc complex. We therefore now report our findings concerning the reactions of sodium N,N-diethyldithiocarbamate with methylene chloride, chloroform, and acetonitrile under strictly anhydrous, oxygen-free conditions.The Nb(V) and T a p ) chlorides and bromides react vigorously and exothermically with Nadtc in methylene chloride to form the appropriate metal-dtc complexes together with varying amounts of an organic product analyzing for C, ,H22N2S,. Formation of the organic product is suppressed if the reaction mixture is cooled below reflux temperatures and the Nadtc added slowly. With the corresponding metal iodides, the complex formation is very slow but the reaction mixture, on vigorous agitation at room temperature for long periods, gives the expected complex and moderate yields of the organic product. If the reaction mixture is heated under reflux, the organic product is formed in almost quantitative yield to the virtual exclusion of the metal-dtc complex. That the complex is not an intermediate in the formation of the organic product is shown by the fact that mixtures of Nadtc and methylene chloride give excellent yields (> 90 %) of the organic material on heating ...

Reactions between niobium(V), tantalum(V), and protactinium(V) chlorides and bromides and sodium N,N-diethyldithiocarbamate (Nadtc) have been examined in non-aqueous, non-oxygenated organic solvents. Complexes obtained are of the types Mdtc4X, Mdtc3X2, Mdtc3S, Mdtc2X3, and Mdtc2X3.nC6H6 (n = 0.7-1.0); not all complexes have been isolated for each metal. W~thln each group the niobium(V) and tantalum(V) complexes are isostructural; possible structures are discussed in the light of results from infrared (i.r.) and nuclear magnetic resonance (n.m.r.) spectra, molecular weight, and electrical conductivity measurements. IntroductionAs part of our studies (1) on reactions between sodium N,N-diethyldithiocarbamate (Nadtc) and anhydrous metal halides in non-aqueous solvents, we have studied reactions (which have been the subject of a preliminary communication (2)), involving the niobium(V), tantalum(V), and protactinium(V) halides. Almost all of the work on dithiocarbamate complexes of these elements has been reported only recently (3). For example, it has been shown (4) that carbon disulfide can be inserted into the niobium(V) and tantalum(V) pentamides forming, in the latter case Tadtc, (dimethyl derivative) while the niobium(V) pentamide is reduced, Nbdtc, being the final product. The reduction is thought to occur because of the steric strain imposed on an intermediate complex, Nbdtc,, which liberates a dithiocarbamate radical; the latter subsequently forms tetramethyl thiuram disulfide. This is one of the relatively

Durch Oxidation der polytertiären Phosphine (I) und (IIIa) und des Phosphinarsins ′ (IIIb) mit Wasserstoffperoxid in Benzol werden in 90‐95%iger Ausbeute die Oxide (II) bzw. (IV) erhalten.