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  • Title: Transition metal-carboryne complexes: synthesis, bonding, and reactivity.
    Author: Qiu Z, Ren S, Xie Z.
    Journal: Acc Chem Res; 2011 Apr 19; 44(4):299-309. PubMed ID: 21395260.
    Abstract:
    The construction and transformation of metal-carbon (M-C) bonds constitute the central themes of organometallic chemistry. Most of the work in this field has focused on traditional M-C bonds involving tetravalent carbon: relatively little attention has been paid to the chemistry of nontraditional metal-carbon (M-C(cage)) bonds, such as carborane cages, in which the carbon is hypervalent. We therefore initiated a research program to study the chemistry of these nontraditional M-C(cage) bonds, with a view toward developing synthetic methodologies for functional carborane derivatives. In this Account, we describe our results in constructing and elucidating the chemistry of transition metal-carboryne complexes. Our work has shown that the M-C(cage) bonds in transition metal-carboranyl complexes are generally inert toward electrophiles, and hence significantly different from traditional M-C bonds. This lack of reactivity can be ascribed to steric effects resulting from the carboranyl moiety. To overcome this steric problem and to activate the nontraditional M-C(cage) bonds, we prepared a series of group 4 and group 10 transition metal-carboryne complexes (where carboryne is 1,2-dehydro-o-carborane), because the formation of metallacyclopropane opens up the coordination sphere and creates ring strain, facilitating the reactions of M-C(cage) bonds with electrophiles. Structural and theoretical studies on metal-carboryne complexes suggest that the bonding interaction between the metal atom and the carboryne unit is best described as a resonance hybrid of the M-C σ and M-C π bonds, similar to that observed in metal-benzyne complexes. The nickel-carboryne complex (η(2)-C(2)B(10)H(10))Ni(PPh(3))(2) can (i) undergo regioselective [2 + 2 + 2] cycloaddition reactions with 2 equiv of alkyne to afford benzocarboranes, (ii) react with 1 equiv of alkene to generate alkenylcarborane coupling products, and (iii) also undergo a three-component [2 + 2 + 2] cyclotrimerization with 1 equiv of activated alkene and 1 equiv of alkyne to give dihydrobenzocarboranes. The reaction of carboryne with alkynes is also catalyzed by Ni species. Subsequently, a Pd/Ni co-catalyzed [2 + 2 + 2] cycloaddition reaction of 1,3-dehydro-o-carborane with 2 equiv of alkyne was developed, leading to the efficient formation of C,B-substituted benzocarboranes in a single process. In contrast, the zirconium-carboryne species, generated in situ from Cp(2)Zr(μ-Cl)(μ-C(2)B(10)H(10))Li(OEt(2))(2), reacts with only 1 equiv of alkyne or polar unsaturated organic substrates (such as carbodiimides, nitriles, and azides) to give monoinsertion metallacycles, even in the presence of excess substrates. The resultant five-membered zirconacyclopentenes, incorporating a carboranyl unit, are an important class of intermediates for the synthesis of a variety of functionalized carboranes. Transmetalation of zirconacyclopentenes with other metals, such as Ni and Cu, was also found to be a very useful tool for various chemical transformations. Studies of metal-carboryne complexes remain a relatively young research area, particularly in comparison to the rich literature of metal-benzyne complexes. Other transition metal-carborynes are expected to be prepared and structurally characterized as the field progresses, and the results detailed here will further that effort by providing easy access to a wide range of functionalized carborane derivatives.
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