Coordination Chemistry of Molybdenum Oxochlorides

Abstract

The coordination chemistry of molybdenum(VI) dioxodichloride, molybdenum(VI) oxotetrachloride, and molybdenum(V) oxotrichloride was studied, and considerable emphasis was placed on derivatives of acetylacetone. From M0O2CI2 it was found possible to synthesize the yellow molybdenyl bisacetylacetonate, M002(0511702)2, and the air-stable amide complexes, MoChCL^L, where L = , -dimethylformamide, , -dimethylacetamide, and , -dibutylacetamide. Molybdenum(V) oxotrichloride was readily prepared by reduction of M0OCI4 with refluxing chlorobenzene. This oxychloride reacted with acetylacetone to give the benzene-soluble acetylacetonate, MoOClCCs^ChL Dimethyl sulfoxide and pyridine reacted wth M0OCI3 to form MoOCl3-2(CH3)2SO and MoOCl^CsHsN. Molybdenum(VI) oxotetrachloride was found to be readily reducible in solution to form adducts containing the M0OCI3 nucleus. Reaction with acetylacetone formed the neutral acetylacetone adduct, MoOCls'CsHgCh, and a similar reaction with benzophenone allowed the formation of M0OCI3• (CeHt^CO. Also, the molybdenum(V) complex, MoOCl3-2C5H6N, was formed by the reaction of M0OCI4 with pyridine. Molybdenum)VI) oxotetrachloride was found to oxidize aromatic compounds with specific coupling in the para position: refluxing phenol formed 4,4 '-dihydroxybiphenyl and refluxing benzene reacted to give poly-/>-phenylene.

Reaction of chromyl chloride with donor molecules

“…Unlike molybdenum and tungsten (14)(15)(16), chromium does not, on presently available evidence, appear to do this in its hexavalent state. Durrant and Durrant (17) describe the crystal structure of chromium trioxide as having the AlF, structure, with sixcoordinate chromium, but Bystrom and Wilhelmi (18) describe the structure as made up of chains of CrO, tetrahedra.…”

Atomic force microscopy of oxidative coupling reactions of phenols with FeCl3 in the solid state

“…1 It can be easily seen from Fig. The solid-solid chemical reactions are as follows ͑Diagram 1͒: a͒ Electronic mail:clbai@infoc3.icas.ac.cn 1͑b͔͒ on the initial ͑001͒ face (R ms ϭ2.305 nm) ͓Fig.…”

“…1 These reactions are faster and more efficient in the solid state than in solution. In general, new solids are prepared just by mixing crystals and the yields are usually extremely high or quantitative without any solvent.…”

Application of molybdenum(VI) dichloride dioxide (MoO2Cl2) in organic transformations

“…Thus, MoO 2 Cl 2 can form complexes with suitable ligands to provide hexacoordinated geometries. 15 Hepta-coordinated structures are also claimed e.g. with benzyl amine as ligand.…”