Trialkyl- or triaryl phosphines

Besides the thiocyanates, just mentioned, other 5-donor complexes which are of interest are the dialkyl sulfides, [MCl3(SR2)3], produced by the action of SR2 on ethanolic RhCl3 or on [IrClg] ". Phosphorus and arsenic compounds are obtained in similar fashion, and the best known are the yellow to orange complexes, [ML3X3], (M = Rh, Ir X = Cl, Br, I L = trialkyl or triaryl phosphine or arsine). These compounds may exist as either mer or fac isomers, and these are normally distinguished by their proton nmr spectra (a distinction previously made by the measurement of dipole moments). An especially... 

This is an extremely useful reaction for the synthesis of alkenes. It involves the addition of a phosphonium ylid, e.g. (136), also known as a phosphorane, to the carbonyl group of an aldehyde or ketone the ylid is indeed a carbanion having an adjacent hetero atom. Such species are generated by the reaction of an alkyl halide, RR CHX (137), on a trialkyl- or triaryl-phosphine (138)—very often Ph3P—to yield a phosphonium salt (139), followed by abstraction of a proton from it by a very strong base, e.g. PhLi ... 

The need for higher product specificity and milder reaction conditions (see also Section IX) has led to extensive research in hydroformylation technology. This research, as reported in technical journals, patent literature, and commercial practice has been primarily concerned with catalysis by rhodium, in addition to the traditional cobalt, and with catalyst modification by trialkyl or triaryl phosphines. These catalyst systems form the basis for the major portion of the discussion in this chapter some other catalyst systems are discussed in Section VIII. 

Shell Chemical has a process that does both the Oxo reaction and hydroformyiation in one step in the same reactor. They use a special catalyst, thought to be cobalt modified with a trialkyl or triaryl phosphine ligand— but they are holding this one pretty close to the vest. Overall yields are 70-80%, with straight-chain alcohols representing greater than 80%. Major by-products are paraffins that are recovered and used to make olefins and then recycled back as feed. This process can also use internal olefins (with the double-bond somewhere besides the alpha position) and yield similar normakiso alcohol ratios. ... 

Ci Hg P. In terms of the shift in CO stretching frequencies in phosphine metal carbonyl complexes, PH3 is less basic (or more 7r-acid) than trialkyl or triaryl phosphines (7, 8, 9).) The results, reported in this chapter, lead to the following significant conclusions. 

From the up-to-date literature and patent review of catalysts used In anhydride and phenolic cured epoxy molding compounds, It Is evident that Imidazoles and their derivatives predominate (Table I). Metal complex, trialkyl or triaryl phosphines and their complexes, Lewis acids such as zinc or stannous octoate are used to a much lesser extent (Table II). There are a few examples of tertiary amines and urea derivatives used. 

In the [(S4)(Mo2E2S2)(S2)] " complexes, the easily polarizable rj -82 ligands also react readily with nucleophiles such as trialkyl or triaryl phosphines and are more reactive than the 17 -84 ligands. The abstraction of 8 with PhsP, from the (S2)Mo=S and (82)Mo=0 units... 

Compounds of Ni(II), Pd(II) and Pt(II) - fulminates with trialkyl- or triaryl-phosphine are formed by the reaction of the tetrafulminato complexes with the corresponding phosphine ... 

Many representatives of the trialkyl orthophosphate ester, dialkyl alkyl (or aryl) phosphonate ester, alkyl dialkyl (or diaryl)-phosphinate, and trialkyl (or triaryl) phosphine oxide class have been investigated. Judging from the reviews available, none of the more exotic types appears to offer any particular advantage over tributyl orthophosphate as a selective extractant for resolving lanthanide mixtures. Most are either viscous liquids or solids that require a diluent, and for the most part the individual separation factors to be had are unspectacular. 

Preparation.- Trialkyl or triaryl phosphites and trithiophosphites (55) can be obtained in 50-90% yields from white phosphorus, carbon tetrachloride, triethylamine, and the appropriate alcohol, phenol, or thiol in a polar aprotic solvent such as dimethylformamide. A series of racemic phenylbis(dialkylamino)phosphines (56) have been prepared in a one-pot synthesis as shown the bulk of the dicyclohexyl-amino group prevents substitution of the second chlorine atom, and the products (56) are claimed to be stable to air and moisture. In a one-pot synthesis tris(diethylamino)-phosphine has been treated successively with three different alcohols to give a 89% yield of the thiophosphate (57) after oxidation with sulphur. ... 

Aminophosphines. - The bis(V-pyrrolidinyl)phosphines (139), prepared conventionally by treatment of the appropriate organodichlorophosphine with an excess of pyrrolidine, have proved to be unusually electron-rich <7-donor ligands when compared to either tris(V-pyrrolidinyl)phosphine, or trialkyl-and triaryl-phosphines. Full details of a route to the polycylic aminophos-phirane systems (140) have now appeared. The bis(aminophosphine) (141) has been prepared and used in the synthesis of macrocyclic metal complexes. Two new chiral aminophosphine systems (142) and (143) have been prepared by transamidation of related aryl bis(dimethylamino)phosphines with a chiral amine. The chiral aminophosphine (144) has been obtained from the reaction of chlorodiphenylphosphine with the methyl ester of alanine. A range of ether-functionalised aminophosphines (145) has also been prepared. 

The trialkyl or triaryl phosphite complexes are more accessible than those of tertiary phosphines. The phosphite ligands complex strongly to rhodium, and easily displace alkene, alkadiene and even carbonyF ligands from [RhCl(CO)2]2 (equations 41 and 42), a displacement that cannot be achieved by tertiary phosphines. Indeed, even tertiary phosphine ligands themselves can be displaced by the phosphite ligands (equation 43).The phosphite complexes can also be prepared by cleaving [RhX(P(OR)3 2]2 complexes with additional ligand (equation 26). 

Phosphites convert phosphinic acids into their esters (6.259) with Grignard reagents, phospho-nous esters can be obtained (6.238). Trialkyl or triaryl phosphites react with a diketones to produce a variety of pentaoxyphosphoranes known as 1,3,2 dioxaphospholes (6.963) (Section 6.23). 

A convenient method of preparing trialkyl and triaryl phosphines in the laboratory is to use organolithium or Grignard reagents. Mixed phosphines R PR and R2PR can also be made in this way, starting from R PCl or R PCl instead of from PCI3. 

Hydroxy(alkoxy)phosphonium Ions. Olah and McFarland560 studied the protonation in HS03F or HS03F-SbF5 solution of varied phosphorus oxyacids and derivatives. Treatment of tetravalent phosphoms compounds (phosphorus, phosphonic, and phosphinic acid and their trialkyl and triaryl derivatives) results in (9-protonation and the formation of hydroxyphosphonium ions. Trivalent phosphites, in turn, are protonated at the phosphorus atom. The 31P shifts observed for the latter ions are significantly deshielded, which was attributed to significant oxonium ion character. 

The alkynylation of phosphorus nucleophiles has been less investigated (Scheme 7). Ochiai and co-workers first demonstrated in 1987 that the alkynylation of triphenyl-phosphine was possible with alkynyliodonium tetrafluoroborate salts under light irradiation (Scheme 7, A) [69]. The reaction most probably involves radical intermediates. In 1992, Stang and Critell showed that light irradiation was not needed if alkynyliodonium triflates were used [70]. Later, this methodology could be extended to other triaryl- or alkyl phosphines [71, 72]. In 1990, Koser and Lodaya also reported the synthesis of alkynylphosphonates by the Arbusov reaction of alkynyliodonium tosylates with trialkyl phosphites (Scheme 7, B) [73]. Alternatively, the same compotmds can be obtained by the reaction of alkynyliodonium tosylates with sodium phosphonate salts [74]. 

---