Internal metallic complexes

Complexes of bulky phosphines and internal metallation reactions... 

When complexes of bulky tertiary phosphines are heated, internal metal-carbon bond formation frequently occurs (Figure 3.50). 

Detailed kinetic studies of the decomposition of platinum(II) dineophyls show (Figure 3.60) the exclusive formation of t-butylbenzene and an internally metallated platinum complex (3,3-dimethylplatininadan). 

This ability to grow in polluted soils and withstand high heavy metal concentrations rests on complex mechanisms involving both avoidance through exclusion of metal ions from the cytoplasm and tolerance of high internal metal concentrations (126), this being often dependent on the induction of specific genes and proteins (126,127). 

Therefore the most common homoleptic bis-dithiolene metal complexes [Mn(S2C2R2)2]n" (M = Ni, Pd, Pt) can potentially take part in the redox sequence illustrated in Scheme 7. Once again, this has to be considered a simplified sequence in that the occurrence of internal metal-to-ligand electron transfer cannot be ruled out. 

As far as the fullerene internal structure is concerned, there is little change on metal complexation. The metal bound transannular [6,6] bond is elongated relative to the remaining fullerene C=C bonds. It often attains a length (=1.5 A) comparable with that of other C—C bonds such as the transannular [6,5] bond or those for an analogous alkene complex. The structure often is described as metallacyclopro-... 

Treatment of truns-[PdCl2(PhCN)2] with biacetyl-bis(N-methyl, N-phenyl)osazone (L) in CH2C12 yields the square-planar osazone complex [PdCl2L], which under suitable conditions loses HC1 to yield the internally metallated complex (23), the structure of which has previously been determined.76,77 Studies of the condensation... 

Interest in the internal metallation ability of the bulky dimethyl-(l-naphthyl) phosphine has stimulated an extension of previous work89 with the preparation of the complexes [MX2 EMe2 (l-naphthyl) 2] (M = Pd or Pt X = Cl, I, or Me E = P or As)90. Although the Pt halide complexes showed no tendency to undergo internal metallation even on prolonged heating, the methyl analogues readily evolved CH4... 

A related reduced series (Figure 5.5) was also reported J74 Selectivity of these crowned arborols (100-102) towards alkali metal cation binding was examined and allosteric as well as conformational binding effects were studied. Also they showed that the sterically less crowded arborols (e.g., 102) are better for the dissolution of myoglobin in organic solvents, such as DMF. This example affords an interesting entrance to internal metal ion complexation at a specific loci see Section 8.3. 

Electrochemical reduction of [RuCl(dppp)2]PF6 affords unstable anionic complexes which rapidly internally metallate to give [RuH(C6H4P(Ph)(CH2)3PPh2)(dppp)].1509a Direct synthesis of this com-... 

The internally metallated iridium(I) complex (51) results from treatment of [Ir(Cl)(PPh3)3] with 1-Li-2R-1,2-BI0C2H,0(R = Me, Ph) in ether. The reaction presumably proceeds by initial formation of a carborane iridium(I) complex (49), which is transformed to (51) via the intermediate species (50)... 

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