Ylides, phosphorus ylide complexes

Trzcinskabancroft, B., Knachel, H., Dudis, D., Delord, T.J. and Marler, D.O. (1985) Experimental And Theoretical-Studies Of Dinudear Gold(I) And Gold(II) Phosphorus Ylide Complexes - Oxidative Addition, Halide Exchange, And Structural-Properties Including The Crystal And Molecular-Structures Of [Au (CH2)2PPh2]2 And [Au(CH2)2PPh2]2(CH3) Bri. Journal of the American Chemical Society, 107(24), 6908-6915. 

Basil et al. [518] have studied theoretically and experimentally dinuclear phosphorus ylide complexes of Au(I) and Au(II). These compounds revealed irreversible redox behavior in CV experiments. 

Ni phosphorus-ylide complexes were reported by Ittel and co-workers to be active for the co-polymerization of ethylene and non-vinyl-functionalized monomers, yielding functionalized polyethylenes (PEs). These results demonstrate the high potential of late transition metal complexes for the production of co-polymers from hydrocarbon and polar monomers. 

The phosphorus ylide complex [(Ph3PCH2)2Au]2Ag2(C104)4 445 also contains Au-Ag bonds [(2.783(2)/2.760(2) A] unsupported by any covalent bridge within a Au2Ag2 ring, but each silver atom is further bonded to two oxygen atoms from two... 

The majority of gold(I) ylide complexes prepared have been of a binu-clear constitution. The first compound of this type was obtained (56) when [Au(CH2PMe3)2]Cl was allowed to stand in the presence of the ylide for seven days [Eq. (19)]. The 3IP-NMR spectrum showed only one signal, indicating that the two phosphorus centers were in identical environments, and the H-NMR spectrum exhibited two doublets with 2/(P—CH3) and 2J(P—CH2) having the same sign. Thus the symmetrical structure depicted in Eq. (19) was invoked, and the presence of two onium centers adjacent to the Au—C bonds was believed to stabilize this unlikely species. 

Albanese, J. A. Staley, D. L. Rheingold, A. L. Burmeister, J. L. Synthesis and molecular structure of a dinuclear phosphorus ylide complex /t-dichlorobis[chloro(benzoylmeth-ylenetri-u-butylphosphorane) palladium(I I). 

Monomeric Auu has also been established for unsaturated S-donor ligands such as R2NCS2 and S—C(CN)=(CN)-S , and in the dicarbollyl complex [Au QHn ]2. Most Au" compounds, however, contain metal—metal bonds.43 Good examples are the phosphorus ylide complexes shown in Fig. 18-1-3 (see Section 18-1-10). The cation [ AuCl(dppn) 2]2+ contains a Au11—Au" bond of 2.61 A, unsupported by bridging ligands [dppn = 1, 8-bis-(diphenylphosphino)naphthalene].44... 

In addition to the phosphorus ylide complexes, arsenic and snlfur yUde complexes of silver have been obtained, althongh no structural reports exist. While the arsenic derivatives match the phosphorus ylide complexes for stability of the Ag products, the sulfoxonium ylide complexes are somewhat less stable. 

As outlined in previous volumes, the chemistry of ylides coordinated to noble metals, particularly palladium, platinum and gold continues to attract most attention. Refluxing (dppm)palladium(II) dichloride [dppm = bis(diphenylphosphino)methane] with alkynes in mixtures of 1,2-dichloro-ethane/l,4-dioxane provides a novel route to palladium-bound alkenyl phosphorus ylide complexes (53) (Scheme 1)P The reaction represents the... 

Mononuclear ylide complexes of gold(I) and gold(III) have been obtained in a variety of ways203,204, as detailed below. The largest number of complexes of both gold(I) and gold(III) has been prepared with phosphorus ylides, but species containing arsenic or sulphoxonium ylides have also been reported. Some prototypes are summarized in Table 7. 

TABLE 8. Cyclic voltammetry data (V) of phosphorus ylide complexes... 

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