Phosphines functionalized

Attachment of pyridine- and phosphine-functionalities to oxalamidine ligands has also been achieved. Scheme 199 exemplifies the use of such ligands in the synthesis of novel organopalladium oxalamidinate com-... 

Keywords. Primary phosphines, Thioether phosphines, Amido phosphines, Carboxylate phosphines, Functionalized phosphines... 

The coordination chemistry of tertiary phosphine-functionalized calix[4]arenes have been described.279 Treatment of a bis(diphenylphosphino) or bis(dimethylphosphino) derivative of calix[4]arene with [PtCl2(COD)] leads to the formation of the corresponding dichloroplatinum(II) complex. The related diplatinum(II) species has also been reported with the tetrafunctionalized calix[4]arene.280 The mononuclear derivative is susceptible to oligomerization if the two free phosphine ligands are not oxidized or complexed to another metal center such as gold(I).279 The platinum(II) coordination chemistry of a mono-281 and diphosphite282 derived calix[ ]arene (n = 4 and 6, respectively) has also been described. 

The phosphacyclopentadienes with phosphine function are called 1//-phospholes and they form an important part of contemporary P-heterocyclic chemistry. Phosphole chemistry has undergone an intensive development, which is well demonstrated by the fact that while in the first edition of Comprehensive Heterocyclic Chemistry (1984), only several pages were devoted to phospholes [1], the second edition (1996) discusses this topic in a lengthy chapter [2], Besides these, exhaustive monographs have been published in P-heterocyclic chemistry also incorporating the new developments of phosphole chemistry [3, 4], The first review in the subject was written by Mathey [5],... 

Figure 4.15. Synthesis of phosphine-functionalized carbosilane dendrimers.[31]...

The low affinity of the alkali metals for neutral P-donor ligands has hampered efforts to synthesize complexes in which there is a genuine R3P-M interaction (see Section I). However, this poor affinity may be overcome by incorporating a remote phosphine functionality into a potentially chelating anionic ligand, such as a phosphine-substituted alkoxide, amide, or aryl, and several alkali metal complexes of such ligands have been isolated. 

Selected Structural and NMR Data for Crystallographically Characterized Alkali Metal Complexes of Tertiary Phosphine-Functionalized Ligands... 

Phosphine-Functionalized Amphiphlles for Rhodium-Catalyzed Hydrogenation... 

The phosphine-functionalized tpy ligand 4 -Ph2Ptpy has both hard and soft donor sites the ligand is prone to oxidation to 4 -Ph2P(0)tpy and this affects the method of preparation of [Ru(4 -Ph2Ptpy)2]. " The complex [RuL(4,4 -Me2bpy)(NCS)] where L = 4-phosphonato-2,2 6, 2"-terpyridine, shows two ground-state pKi values at 6.0 and <4.0. The emission spectrum of the complex and the excited-state lifetimes are pFI-dependent. ... 

De Groot et al. (18) prepared phosphine-functionalized carbosilane dendrimers of different generations (4, 8, 24, and 36 phosphine end groups) and used their palladium complexes as catalysts for the allylic alkylation of allyl trifluoroacetate with diethyl sodio-2-methylmalonate. 

Reetz et al. 16) were the first to recover and recycle a dendritic catalyst through a precipitation procedure. The dimethylpalladium complex of the phosphine-functionalized DAB-dendr-[N(CH2PPh2)2]i6 dendrimer (la) is an active catalyst for the Heck reaction of bromobenzene and styrene to give trara-stilbene (89% trans-stilbene and 11% 1,1-diphenylethylene, at a conversion of 85—90%, Scheme 8). 

Rhodium complexes of the phosphine-functionalized carbosilane dendrimers are active for the hydroformylation of alkenes. The influence of the flexibility of the dendritic backbone on the catalytic performance was characterized by comparing dendritic ligands 84a-84c (conditions toluene, 80°C, 20 bar CO/H2) 49). 

Phosphines Functional groups Solvents Products Distribution (%)... 

A new type of triaryl phosphine-functionalized imidazolium salt containing cations such as (6) has been prepared. Palladium complexes of (6) generated in situ have been used successfully in Heck-type reactions of aryl halides with acrylates and of 4-bromotoluene with styrene derivatives.34 The first Heck-type reaction of aryl halides with allenes has been reported. 1,3-Double arylations were observed with 3-substituted-l,2-allenyl sulfones, while 1-monoarylation was favoured with 3,3-disubstituted-l,2-allenyl sulfones.35 It has been shown that the a-arylation of methane-sulfonamides (7) may be achieved using palladium catalysis reaction proceeds through the sulfonamide enolates.36 It is also reported that palladium cross-coupling of alkynes with /V - (3 - i odophe n y I an i I i ncs) may lead to the formation of substituted carbazoles.37... 

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