Phosphines macrocyclic

The synthesis of a manganese(I) complex of the macrocyclic phosphine ligand l,5,9-triethyl-l,5,9-triphosphacyclododecane (L) has been reported. Thus, reaction of L with Mn(CO)5Br yields MnL(CO)2Br whose six-coordinate structure was confirmed by X-ray diffraction. 

There are four comprehensive reference texts on phosphine coordination chem-istry. Two are somewhat out-of-date, but the article by Levason is more recent. However, all four give much useful information on synthetic procedures for the preparation of primary, secondary and tertiary phosphines diphosphines multidentate and macrocyclic phosphines mixed Group 15 donor and mixed Group 15/16 donor systems and phosphorus-containing heterocycles. The coordination chemistry of phosphorus has expanded to include P4 fragments, Pg rings, and even naked phosphorus atoms, for example, nine-coordinate P and -Pg systems. ... 

The two families of macrocyclic phosphine oxide disulfoxides (100 X = (CH2)2, 1,2-xylyl, 1,3-xylyl) and (101 X = (CH2)3 s, 1,2-xylyl, 1,3-xylyl) have been prepared stereoselectively for comparisons of three-point binding abilities with monoalkylammonium ions <92TL2107, 93PAC461, 93JA7900). Compound (101 X = 1,2-xylyl) also binds halide ions <94JA4069>. 

A variation of the receptor polarization effect is the binding strategy shown by schematic Complex 9. In this case the binding of an ion to one face of an appropriately designed receptor polarizes (and perhaps preorganizes) the receptor so that it can bind the counterion to the opposite face with increased affinity. Two examples that use this strategy are the macrocyclic phosphine oxide 10, which can simultaneously bind a monoalkylammonium cation and Cf J " and the cyclopeptide 11, which simultaneously binds an alkyltrimethylammonium cation and tosylate anion " (Chart 2). 

Scheme 4 Preparation of macrocyclic phosphinic acids 29 and 29 analogues to Ciluprevir...

Scheme 5 Preparation of macrocyclic phosphinic acid 32 analogue to MK-7009...

Jeffery J. C., Odell B., Stevens N. and Talbot R. E., 2000. Self assembly of a novel water soluble iron(II) macrocyclic phosphine complex from tetrakis(hydroxymethyl)phosphonium sulfate and iron(II) Ammonium sulfate Single crystal X-ray structure of the complex. Chem. Comm. 101-102. 

Unlike their nitrogen analogues, homoleptic macrocyclic phosphines represent a rare class of ligands. Some of the apparent lack of interest relates to the difficulty of their preparation and, for most derivatives, their inherent instability to air. 

The 14-membered macrocyclic phosphine 77 and corresponding sulfide 78 were prepared by the macrocyclization under high dilution conditions and further oxidation with sulfur (Scheme 12.29). Both ligands were used as ionophores in an all-solid state poly(vinylchloride) matrix membrane electrode. The sulfide 78 based electrode exhibited a Nemstian response towards copper (II) ions with a cationic slope of 30.7 mV/pCu and a detection limit of 5.97 x 10 M. The potential response remains almost unchanged over the pH range 3.9-6.4 at least 7 months. Sensors based on the macrocycles 77 and 78 demonstrate the copper (11) ion sensitivity over other metal ions [83]. 

Bartsch R, Hietkamp S, Morton S et al (1983) Reactions of coordinated ligands. 12. Single-stage template syntheses of tetradentate macrocyclic phosphine complexes. Inorg Chem 22 3624-3632... 

Bauer EB, Ruwwe J, Martln-Alvarez JM et al (2000) Olefin metatheses in metal coordination spheres novel trans-spanning bidentate and facially-spanning tridentate macrocyclic phosphine complexes. Chem Common 2261-2262... 

Sinyashin OG, Karasik AA, Hey-Hawkins E (2008) New synthetic approaches to chiral cyclic and macrocyclic phosphine ligands. Phosphorus Sulfur Silicon Relat Elem 183 445-448... 

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