Thorium thiocyanate

Thorium compounds of anionic nitrogen-donating species such as [Th(NR2)4], where R = alkyl or sdyl, are weU-known. The nuclearity is highly dependent on the steric requirements of R. Amides are extremely reactive, readily undergoing protonation to form amines or insertion reactions with CO2, COS, CS2, and CSe2 to form carbamates. Tetravalent thorium thiocyanates have been isolated as hydrated species, eg, Th(NCS)4(H20)4 [17837-16-0] or as complex salts, eg, M4 Th(NCS)g] vvH20, where M = NH, Rb, or Cs. 

It has also been argued10,40 that the second mechanism (rapid, reversible interconversion of II and IV) cannot be general. The basis for this contention is the fact that electrophilic catalysis is rare in nucleophilic aromatic substitution of non-heterocyclic substrates, an exception being the 2000-fold acceleration by thorium ion of the rate of reaction of 2,4-dinitrofluorobenzene with thiocyanate... 

Isobutyronitrile has been prepared by a number of catalytic vapor-phase reactions at elevated temperatures isobutylamine over copper 2 or nickel,3 isobutyramide over alumina,4 a mixture of ammonia and isobutyraldehyde over thorium dioxide,5 and a mixture of ammonia and isobutyl alcohol over copper. Isobutyronitrile also has been obtained by decarboxylation of 2-methyl-2-cyanopropanoic add 7 and from the reaction of iso-butyric acid with potassium thiocyanate.8 The above procedure is a modification of the method used by Walter and McElvain.9... 

The compounds (Et4N)4[M(NSCe)a] (M = Pa, U) have been characterized by comparing their spectral and crystallographic properties with the corresponding thiocyanate complexes (26). Some thorium(IV) complexes have been prepared containing DMF and N-bonded seleno-cyanate groups (326). Although various uranyl selenocyanate complexes have been reported, no structural data are available (686). 

Neutral complexes of the thiocyanate ligands can be isolated as Lewis base adducts. Thorium and uranium form tetra(hydrate) complexes An(NCS)4(H20)4. The compound U(NCS)4(piper-azine) has been reported. The neutral adducts Th(NCS)4(L)4 and U(NCS)4(L)3 (L = N,N-diisopropylpropionamide) have been structurally characterized. The smaller size of the uranium ion is reflected in the isolation of a seven-coordinate compound, while an eight-coordinate thorium compound is formed. If more sterically demanding carbamide ligands are employed (L = N,N-diisopropylbutyramide, L = 7V,VV-dicyclohexylacetamide), seven-coordinate thorium complexes, Th(NCS)4(L)3 and Th(NCS)2Cl2(L )3, can be isolated. " ... 

Testing explosives, 103, 111 Thiocyanates, 82 Thorium oxide, catalytic, 13, 29 Titanium nitride, 58 Tolite, 102 Tonite, 113 Torpedoes, 96 Trace tests, in... 

Pyrazolin-5-ones form complexes with both inorganic and organic compounds much more readily than do the 2-pyrazolin-5-ones. The most extensive series of complexes is that formed with a variety of metallic salts. Antipyrine (2,3-dimethyl-l-phenyl-3-pyrazolin-5-one) forms a series of complexes with salts of divalent, trivalent and tetra-valent metals. Two molecules of antipyrine form a complex with one molecule of copper, cadmium, cobalt and zinc salts.266,866,1116 Complexes prepared from metallic nitrates are usually hydrated.1322 There also exists a series of complexes in which three molecules of antipyrine form a complex with one or two molecules of metallic salts. Such complexes form with two molecules of simple ferric salts272 or with one of complex iron cyanides.608 Nitrates of thorium, lanthanum, cerium and samarium also give such complexes.841 This ratio also occurs in some antipyrine complexes with cadmium and zinc thiocyanate.266 A number of salts of rare earths and iron which have complex anions such as thiosulfate, thiocyanate, dithionic acid and complex iron cyanides form complexes in which six molecules of antipyrine are present.405,408 608,841,950 Stannic chloride forms salts containing three or four molecules of antipyrine and hydrochloric acid.46... 

Thorium has been sorbed on strongly basic anion-exchangers as the nitrate complex most other metals are not retained [15-19]. Other media employed include chloride [20], sulphate [2], thiocyanate [21], and citrate [22]. In numerous cases, mixed aqueous-organic... 

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