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Molybdenum hexacarbonyl is a popular reagent in academic research. [6]One or more CO ligands can be displaced by other ligands. [7] Mo(CO) 6, [Mo(CO) 3 (MeCN) 3], and related derivatives are employed as catalysts in organic synthesis for example, alkyne metathesis and the Pauson–Khand reaction.
Mo(CO) 6 reacts with arenes to give piano-stool complexes such as (mesitylene)molybdenum tricarbonyl. Cycloheptatrienemolybdenum tricarbonyl, which is related to (arene)Mo(CO) 3, reacts with trityl salts to give the cycloheptatrienyl complex: [3] (C 7 H 8)Mo(CO) 3 + (C 6 H 5) 3 C + → [(C 7 H 7)Mo(CO) 3] + + (C 6 H 5) 3 CH Structure of ...
The six CO ligands are terminal and the Mo-Mo bond distance is 3.2325 Å. [2] The compound is prepared by treatment of molybdenum hexacarbonyl with sodium cyclopentadienide followed by oxidation of the resulting NaMo(CO) 3 (C 5 H 5). [3] Other methods have been developed starting with Mo(CO) 3 (CH 3 CN) 3 instead of Mo(CO) 6. [4]
(Mesitylene)molybdenum tricarbonyl arises from the reaction of molybdenum hexacarbonyl with hot mesitylene: [1]. Mo(CO) 6 + (CH 3) 3 C 6 H 3 → Mo(CO) 3 [(CH 3) 3 C 6 H 3] + 3 CO It can also be synthesized, with good yields by displacement of pyridine ligands of the trispyridine complex Mo(CO) 3 (pyridine) 3 in the presence of Lewis acids.
The process strips CO ligands from the hexacarbonyl and results in the oxidation of Mo(0) to Mo(II). [5] [6] 2 Mo(CO) 6 + 4 HO 2 CCH 3 → Mo 2 (O 2 CCH 3) 4 + 12 CO + 2 H 2. Trinuclear clusters are byproducts. [7] The reaction of HO 2 CCH 3 and Mo(CO) 6 was first investigated by Bannister et al. in 1960.
The M-CO and MC-O distance are sensitive to other ligands on the metal. Illustrative of these effects are the following data for Mo-C and C-O distances in Mo(CO) 6 and Mo(CO) 3 (4-methylpyridine) 3: 2.06 vs 1.90 and 1.11 vs 1.18 Å. [5]
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Compounds that obey the 18-electron rule are typically "exchange inert". Examples include [Co(NH 3) 6]Cl 3, Mo(CO) 6, and [Fe(CN) 6] 4−. In such cases, in general ligand exchange occurs via dissociative substitution mechanisms, wherein the rate of reaction is determined by the rate of dissociation of a ligand. On the other hand, 18-electron ...