Other Ligands between Metal Atoms

Migration of Other Ligands between Metal Atoms 

Isomeric bis(trimethylstannyl) dihydropentalenes have been shown by H NMR spectra to exhibit suprafacial metallotropic rearrangements which 

Finally, a report has been made of a disilver(I) complex with bridging CH2(PPh)2 ligands which exhibits intramolecular intermetal exchange of P atoms in the intermediate temperature range 253-293 K. Above 293 K an intermolecular ligand exchange occurs/ 

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Migration of Other Ligands between Metal Atoms. 355... 

Many other shapes are possible for complexes. The simplest are linear, with coordination number 2. An example is dimethylmercury(O), Hg(CI l,)2 (4), which is a toxic compound formed by bacterial action on aqueous solutions of I Ig ions. Coordination numbers as high as 12 are found for members of the / block, but they are rare in the d block. One interesting type of d-mctal compound in which there are 10 links between the ligands and the central metal ion is ferrocene, dicyciopentadi-enyliron(O), [Fe(C5H5)2] (5). Ferrocene is an aptly named sandwich compound, with the two planar cyclopentadienyl ligands the bread and the metal atom the filling. The formal name for a sandwich compound is a metallocene. 

In nickel and palladium dithiobenzoato complexes, four-membered chelate rings are formed (366), whereas, in the corresponding phenyl-dithio acetates [M2(S2CCH2Ph)4], the dithio ligands act as bridging groups between the two metal atoms, with the formation of binuclear units (367). The molecular structure of the latter compounds shows that each metal atom is coordinated to four sulfur atoms and to the other metal atoms in a square-pyramidal geometry. Other evidence for... 

The thiocyanate ion provides an interesting test of these ideas. In the SCN ion, the sulfur atom is considered to be a soft electron donor, whereas the nitrogen atom is a much harder electron donor. Accordingly, Pt2+ bonds to SCN- at the sulfur atom, whereas Cr3+ bonds to the nitrogen atom. Uncharged metal atoms are considered to be soft electron acceptors, and they form complexes with soft ligands such as CO, 11, and PR3. We will see many examples of such complexes in later chapters. On the other hand, we would not expect complexes between uncharged metal atoms and NH3 to be stable. 

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