Assembling Heterometals through Oxygen: An Efficient Way To Design Homogeneous Catalysts

Abstract

Assembling a molecule containing two metal centers with entirely different chemical properties remains a synthetic challenge. One of the major motivations for this chemistry is its ability to catalyze various organic transformations. The proximity between two different metals in a heterometallic complex allows more pronounced chemical communication between the metals and often leads to the modification of the fundamental properties of the individual metal atoms through the well-known cooperative interaction. Although various types of heterometallic systems are known, the M−O−M′ framework is particularly important because it brings the metals into close proximity with each other. In this Account, we describe several suitable synthetic routes for the assembly of heterometals of entirely different chemical properties through an oxygen atom. The new synthetic strategies for the construction of heterobimetallic complexes take advantage of unprecedented syntheses of a number of hydroxide precursors of the type LMR(OH) [L = CH{N(Ar)(CMe)}2, Ar = 2,6-iPr2C6H3; M = Al, Ga, or Ge; R = alkyl, aryl, or lone pair of electrons], [LSr(μ-OH)]2·(THF)3, and Cp*2ZrMe(OH). We used the Brønsted acidic character of the proton in the M(O−H), Sr(O−H), or Zr(O−H) moiety, to build a new class of heterobimetallic complexes based on M−O−M′ motif. This synthetic strategy assembles a main group element with another main group element, a transition metal, or a lanthanide metal. This synthetic development provides access to a new class of heterobimetallic complexes through oxygen bridging. In many cases these complexes prove to be excellent candidates for polymerization of monomers including ε-caprolactone, ethylene, and styrene. Some of these catalysts bear a chemically grafted methylalumoxane (MAO) unit in the backbone of an active metal center, which led to efficient ethylene polymerizations at an unusually low MAO concentration. We attribute this reactivity both to the presence of a chemically grafted (Me)Al−O backbone in the active catalysts (a part of externally added cocatalyst, MAO) and to the enhanced Lewis acidity from the bridging oxygen at the active metal center. In addition, we have demonstrated the development of heterometallic systems having two catalytically active centers. Such structures could aid in the development of a catalytic system bearing two active centers with different chemistries.