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Main Group Chemistry on a Metal Framework: Reactions of - (R=H, CH3) with Lewis Bases
Housecroft, Catherine E.,Fehlner, Thomas P.
, p. 4867 - 4873 (2007/10/02)
The reactions of - (R=H, CH3) with Lewis bases (L=CO, PhMe2P, NEt3, and H2O) are explored.For R=H and L=PhMe2P, substitution via H2 rather than CO elimination to yield -, Fe(CO)3(PhMe2P)2, and a ferroborane anion spectroscopically characterized in situ.The fragmentation pathway predominates in the presence of excess Lewis base, whereas H2 elimination is favored by low ligand levels.For L=PhMe2P the H2 displacement pathway is promoted with R=CH3.A kinetic study for L=PhMe2P reveals a first-order rate dependence on both substrate and ligand for fragmentation, suggesting associative activation.The dual-fragmentation path observed illustrates competitive base displacement of isoglobal fragments from a single cluster.An analysis at intermediate ligand levels results in the definition of base-promoted cluster substitution via H2 elimination.Under the conditions explored here, CO yields only H2 displacement, H2O only fragmentation, and NEt3 adduct formation with slow fragmentation but no H2 displacement.
