Molybdenum complexes halide

Treatment of these phosphinidene complexes with R CHO afforded RP = C(H)R this is an alternative route to phosphaalkenes.The reaction of (Me3SiN)3N Li3 with M0CI4 or WCI4 gave [ (Me3SiN)3N MCl] (M = Mo or The molybdenum(IV) halide... 

Susuki and Tsuji reported the first Kharasch addition/carbonylation sequences to synthesize halogenated acid chlorides from olefins, carbon tetrachloride, and carbon monoxide catalyzed by [CpFe(CO)2]2 [101]. Its activity is comparable to or better than that of the corresponding molybdenum complex (see Part 1, Sect. 7). Davis and coworkers determined later that the reaction does not involve homolysis of the dimer to a metal-centered radical, which reduces the organic halide, but that radical generation occurs from the dimeric catalyst after initial dissociation of a CO ligand and subsequent SET [102]. The reaction proceeds otherwise as a typical metal-catalyzed atom transfer process (cf. Part 1, Fig. 37, Part 2, Fig. 7). 

Ligand exchange reactions with nitrido molybdenum complex 56 has been documented (Eq. (19)). Treatment of 56 with 2 equiv. of HX (X = Cl or Br) leads to the formation of 57 which, following treatment with triethylamine, afforded 58, wherein a halide has been substituted for the azide ligand found in 56 [27]. The introduction of a nitride onto a Mov complex has been carried out by treatment of Mom or Mo ... 

There are selected examples of the use of additional nitrogen sources such as NSC1, N2, and NC13 (Eqs. (29,30)). The molybdenum nitride halide complexes were isolated from the reaction of a MoVI complex and NSC1 in the presence of Cl- or F [34]. Cummins reported the remarkable reaction of low-valent Mom triamide with N2 (1 atm) to afford the corresponding nitride 80 (Eq. (29)). The presence of bulky amide ligands is critical to the success of the reaction, for it prevents the formation of the stable dimer [(ArRN)3Mo]2. 

In the kinetic interpretation of ECL data presented above the closest approach of reactants has been assumed. It seems to be fulfilled in the case of organic ECL systems (because of the Coulombic attraction between oppositely charged ions). In contrast, in ECL systems involving identically charged transition-metal complexes, Coulombic repulsion may lead to an increase in the electron transfer distance. The molybdenum(II) halide cluster ion MoeCliJ [197-199] is the one of the best-understood examples. In electrochemical reactions MogCliJ is reversibly reduced or oxidized to stable MosCl and Mo6Cl["4 respectively ... 

The lower nuclearity clusters [Mo5Cl13]2 were isolated from MoCls in AlCl3/KCl/BiCl3/Bi melts that led to the hexanuclear species (17). This is the only intermediate isolated from reaction mixture that produces the Mo6C18 4+ core. Solution chemistry has yielded Mo2, Mo3, and Mo4 halide species from mononuclear molybdenum complexes, suggesting that a nucleation process similar to that proposed for the tungsten systems may take place during the formation of hexanuclear molybdenum clusters (18-22). 

Oxo molybdenum complexes such as MoOX4L (X = halide, L = neutral ligand) emit light. The observed emission is a fluorescence. The lowest energy absorption bands in these complexes are due to a 82 transition, and the... 

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