Comprehensive Coordination Chemistry II. Coordination by J. A. McCleverty, T.J. Meyer

By J. A. McCleverty, T.J. Meyer

Finished Coordination Chemistry II (CCC II) is the sequel to what has develop into a vintage within the box, entire Coordination Chemistry, released in 1987. CCC II builds at the first and surveys new advancements authoritatively in over 2 hundred newly comissioned chapters, with an emphasis on present traits in biology, fabrics technology and different parts of up to date clinical curiosity.

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8 A˚) are observed instead. In toluene solution at À80  C, solution, the 1H–6Li HOESY (Heteronuclear Overhauser Enhancement Spectroscopy) spectrum of Li[Me2Si(H)NBut] confirms that the trimeric species lacks Si—H–Li interactions, but two other species with strong Si—H–Li interactions are present also. 233 In contrast, the related magnesium-based compound Mg2[Me2 Si(H)NBut]4 does display evidence of agostic Si—H–Mg contacts in the solid state. 234 The 6pz orbital of the lead in LiPbPh3 is oriented toward the lithium atom, and hence the Pb—Li bond involves the Pb(6pz þ 6s)–Li(2s) orbitals, and not the Pb(6s)–Li(2s) orbitals only.

A Mg4P2 octahedron is at the center, with the phosphorus atoms in a trans position. The Mg–Mg edges are bridged by the P(H)Si(But)3 substituents. A refluxing toluene solution of Mg6[P(H)Si(But)3]4P[Si(But)3]2 will eliminate H2PSi (But)3 and precipitate the hexameric [MgPSi (But)3]6. 454 It is a doubly capped Archimedean antiprism with ten phosphorus centers and a lithium atom located on each deltahedral face. 60 A˚)456,457) but examples of M(P(H)R)n compounds are more common. 244,453,470–473 The triisopropylsilylphosphido ligand has been used to generate a variety of polymetallic species.

The trimethylsilyl groups are associated with hydrocarbon solubility of the base-free and ether adducts. This is a particularly remarkable property, in that the metal atoms in many of the structures are exposed to external molecules, and are not appreciably shielded by the trimethylsilyl group of the amido ligands (see Figure 28). 266 Extensive NMR data (1H, 13C, 15N, 29Si) exist for these species;19 the (N) and (SiMe3) shifts are sensitive to the identity of the metal center. In the case of the alkaline-earth compounds, differences in the chemical shifts and coupling constants for the bridging and terminal –SiN(Me3)2 groups disappear for the barium derivatives, an indication that they are in fast exchange.

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