Calixarene phosphines

Fig. 37.17 Chemical structure of the calixarene-phosphine ligand (a) and graphical representation of the macrocycle capped Au nanoparticle with the Au core diameter of 0.9 nm and five calixarenes bound to metal surface (b). Two calixarenes bind the metal core with two phosphines while the other three with only one phosphine. The monodentate ligand possesses one phosphine bound to the metal surface and one unbounded phosphine oxide (Reproduced with permission from Ref. [106], Copyright 2010, Nature Publishing Group)...

Water-soluble calixarenes are more and more investigated in order to make use of their ability to host other molecules, and the first examples of the use of phosphine-modified calixarenes in organometallic catalysis appeared just recently. Rhodium complexes prepared with 197 (Figure 19)... 

Alkenes and Alkynes. A series of metal carbonyl cations, such as [Au(CO)n]+,287,288 [c-Pd( i-CO)2]2+,289 [Rh(CO)4]+,290 and [(Pt(CO)3)2]2+,291 was found to induce the formation of carboxylic acids from alkenes and CO in the presence of H2SO4 under mild conditions. A novel water-soluble Pd catalyst292 and Pd complexes of calixarene-based phosphine ligands293 showed high activity in the regioselective carboxylation of vinyl arenes to yield 2-arylpropionic acids or... 

Selective Extraction of Actinides by Calixarenes Bearing Phosphine Oxide Moieties... 

Extraction of thorium nitrate and europium nitrate 0 0 4 M) from 1 M HN03 into dichloromethane was carried out for 19 calixarenes totally or partially substituted on the lower rim by phosphine oxide moieties (CPol-CPol7-CPol9-CPo20) and for one calixarene substituted by phosphinate (CP0I8) (see Section 4.7).IM 152 154... 

The replacement of the phenyl groups on the phosphine oxide moieties by n-butyl groups leads to a complete loss of extraction. Increasing the length of the chain linking the calixarene to the phosphine oxide moieties leads to a decrease of extracting ability of both tetramer and hexamer (Table 4.23). The selectively substituted... 

By the end of this chapter you should be familiar with some of the more frequently encountered co-ligands in organometallic chemistry. These include phosphines, nitrosyls, (spectator) cyclo-pentadienyls, carbaboranes, calixarenes, silsesquioxanes, cor-rins and porphyrins... 

Other signiflcant complexes of this type, containing one or more lanthanides, are formed by calixarenes (see Calixarenes) Much of this work has been prompted by their potential in separating lanthanides from uranium and other metals. A calixarene ligand with two amide substituents has been synthesised as an extractant for lanthanides dimeric Sm and Eu and monomeric Eu complexes have been prepared. Another calixarene, with four phosphine oxides attached, has been fixed to silica particles and the resulting system has been found to give very efficient extraction of Eu + and Ce + from simulated waste. A calix[4]arene complex of Gd + binds... 

The cyclic phosphinate (96) has been isolated from the reaction of dichloro(methyl)phosphine with the ethoxycarbonylimine derived from hexafluoroacetone. Treatment of trichloro(organo)phosphonium-hexafluorophosphate salts with dichloro(diethylamino)phosphine results in the halophosphonium salts (97). Some reactions of dichloro(-)menthylphosphine have been reported.As usual, nucleophilic displacement reactions of halogenophosphines have received attention as routes to new systems of interest as ligands.Of particular interest in this connection is a report of the synthesis of the phosphorus-functionalised calixarenes (98). Only one chlorine atom of dichloro(phenyl)-phosphine is replaced on treatment with an excess of dicyclohexylamine, enabling the stepwise synthesis of the chiral aminophosphines (99), described as air-stable solids. 

Phosphine Chalcogenides as Ligands. - The complexation of lanthanide and actinide ions by phosphine oxide ligands remains an active area, and a theoretical assessment of the coordination of phosphine oxides (and phosphate esters) by trivalent lanthanide ions has appeared." Trivalent lanthanide complexes of the functionalised enol phosphine oxide (265), (and a related phosphonate), have been describedComplexes of thorium(iv) with bis(di-phenylphosphino) ethane dioxide and bis(diphenylphosphinoyl)amide have also been characterised." Calixarene systems which bear phosphine oxide... 

Miscellaneous Reactions. Wittig technology has been used to prepare ylide-, phosphate-, phosphite- and phosphinate-terminated dendrimers, and calixarenes bearing pyridyl podands on their upper rim 7°... 

P-5 A phosphinic calixarene is complexed to four Ag(I)Q molecules and one additional chloride ion to give an anion (161) that can act as host for alkali metal cations, Hg(II) and Pb(II)235 236. 

The first bisphosphine calixarenes that have been used in catalysis are di(amide)-phosphine hybrids calix[4]ar-ene. Reaction of [RhCl(norbornadiene)]2 with these calixarene derivatives gave an organometallic complex whose norbornadiene-rhodium moiety lies above the cavity defined by the four substituents of the calixarene and between the two amide functionalities. This complex was applied in the hydroformylation reaction of styrene. The rather low reaction rate observed (7.5 turnovers per Rh per hour) has been attributed to a partial encapsulation of the metal center preventing the approach of the substrate. Indeed, the metal center may be viewed as located in a hemispherical ligand environment. 

Calcium complexes amino acids, 33 arsine oxides, 9 bipyridyl, 13 crown ethers, 39 dimethylphthalate, 16 hydrates, 7, ionophores, 66 peptides, 33 phosphines, 9 pyridine oxide, 9 Schiff bases, 29 urea,9 Calixarenes... 

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