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A series of reports describing the syntheses and structures of [MCl2(diazadiene)] (M = Cr, Mo, W) complexes is reassessed in the context of known chemistry of low-valent Group VI metal complexes, crystallographic trends such as M--CI bond lengths and unit cell volumes, and calculated metal--ligand bond lengths. Crystallographic data and computational results are inconsistent with any of these species being second or third row transition metal complexes. A review of the crystallographic information files accompanying the [MCl2(diazadiene)] (M = Mo, W) published structures reveals that the metal atoms were inappropriately treated with partial site occupancy factors (0.775 for Mo; 0.4005 and 0.417 for W), the effect of which was to manifest lighter-element behavior and better refinement in accord with the metal atoms' correct identity. A deliberate synthesis and characterization by X-ray diflraction of [ZnCl2(MesdadMe)] (MesdadMe = l,4-bis(2,4,6-trimethylphenyl)-2,3-dimethyl-l,4-diaza-1,3-butadiene) are reported. Refinement of this structure with the same combination of second or third row metal and offsetting partial site occupancy is shown to provide final refinement statistics essentially the same as with the correct model employing M = Zn at site occupancy 1.00. Use of the published method for synthesis of [WCl2(diazadiene)] with MesdadMe and [WBr4(MeCN)2] in lieu of [WCl4MeCN2] is shown to produce [ZnBr2(MesdadMe)], which has also been characterized by X-ray diffraction. It is concluded that the unusual putative 12-electron [MCl2(diazadiene)] (M = Cr, Mo, W) complexes are in all cases the corresponding [ZnCl2(diazadiene)] complexes, Zn having been commonly employed as reducing agent in their synthesis. [ABSTRACT FROM AUTHOR]

The reactions of cyclodiphosphazane cis-[tBuNP(OC6H4OMe-o)]2 (1) with 2 equiv of CuX in acetonitrile afforded one-dimensional CuI coordination polymers [Cu2X2{tBuNP(OC6H4OMe-o)}2]n (2, X = Cl; 3, X = Br; 4, X = I). The crystal structures of 2 and 4 reveal a zigzag arrangement of [P(μ-N)2P] and [Cu(u-X)2Cu] units in an alternating manner to form one-dimensional CuI coordination polymers. The reaction between 1 and CuX in a 2:1 ratio afforded mononuclear tricoordinated copper(l) complexes of the type [CuX{(tBuNP(OC6H4OMe-o))2}2] (5, X = Cl; 6, X = Br; 7, X = I). The single-crystal structures were established for the mononuclear copper(l) complexes 5 and 6. When the reactant ratios are 1:1, the formation of a mixture of polymeric and mononuclear products was observed. The CuI polymers (2-4) were converted into the mononuclear complexes (5-7) by reacting with 3 equiv of 1 in dimethyl sulfoxide. Similarly, the mononuclear complexes (5-7) were converted into the corresponding polymeric complexes (2-4) by reacting with 3 equiv of copper(l) halide under mild reaction conditions. [ABSTRACT FROM AUTHOR]