Photosubstitution reactions in potassium octacyanomolybdate(IV) and octacyanotungstate(IV) in the presence of 1,10-phenanthroline and 2,2 [formula omitted]bipyridyl

• Published in: Polyhedron Vol. 4; no. 5; pp. 821 - 827
• Main Authors: Ali, S.I., Murtaza, Zakir
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 1985; New York, NY Elsevier Science
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Photochemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Ligand substitution; Organic ligand; Anionic complex; Transition metal Complexes; Photochemical reaction; Quantum yield; Cyano complex; Tungsten Complexes; Ultraviolet radiation; Hydroxo complex; Medium effect; Content; PH; Aqueous solution; Infrared spectrum; Molybdenum Complexes
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(00)87032-1

Substitution reactions take place following the photonic excitation of aqueous K 4M(CN) 8 (where M = Mo or W) in the presence of 1,10-phenanthroline and 2,2 - ́ bipyridyl. Changes in absorbance with time show that the overall reaction is dependent on photochemical activation of potassium octacyanomolybdate(IV) and -tungstate(IV). The species [K 2Mo(CN) 4(OH) 2(phen)], [K 2W(CN) 4(OH) 2(phen)], [K 2Mo(CN) 4(OH) 2(bipy)] and [K 2W(CN) 4(OH) 2(bipy)] exist in solution. The final photosubstitution products [Mo(OH) 3(CN)(phen) 2] · 2H 2O], [Mo(OH) 3(CN)(bipy) 2] · 3H 2O, [W(OH) 3(CN)(phen) 2] · 2H 2O and [W(OH) 3(CN)(bipy) 2] · H 2O have been isolated in the solid state. Their IR spectra have been discussed. The quantum yield of the photosubstitution reactions has been determined and its variation with change of concentration of the complex as well as the H + ion concentration has been studied.