Polyphosphinate

Phosphonitrilic Metal polyphosphinates Phenylsilesesquioxanes (phenyl-T ladder polymers)... 

The yielded product can be converted to a surface-active compound if at least one ester group has been transformed to the free acid or an alkali metal salt thereof [160]. There are also many compounds from phosphinic acid derivatives claimed to be useful as sequestrants and builders to improve detergency, especially bisphosphonylmethylphosphinic acids and polyphosphinic acids [structures (9) and (10)], respectively ... 

Polyphosphinic acids are obtained by an Arbusov reaction from chloro-methylphosphonites in the presence of tertiary amines [161] see Eqs. (89)—(91) ... 

Chelating di- or more generally, polyphosphines may also be used as sta-bihzers of nanoparticies. Reactions with rutheniiun and palladium show that... 

Another example of selective C=C bond hydrogenation has arisen from mechanistic studies on an iron m-hydride dihydrogen complex, [Fe(PP3)(FI)(H2)](BF4) [PP3 = P(CH2CH2PPh2)3], a catalyst inactive with alkene substrates. Scheme 6 shows that no decoordination of dihydrogen is required in any step of the cycle and that the vacant site is created by unfastening of one of the P-donor atoms (species (16)).50 Extensive studies on catalytic alkene hydrogenation by analogous tripodal (polyphosphine) Rh, Os, and Ir complexes have been carried by Bianchini and co-workers.51,52... 

Fig. 3 Cyclic and differential voltammograms of polyphosphine-linked Ru3 cluster dimer 28, trimer 29 and tetramer 30, recorded in 0.1M dichloromethane solution of (Bu4N)(PF6). The scan rate is lOOmVs-1 for CV and 20mVs-1 forDPV...

The complex consists of a bis(diphosphinomethanide) ligand binding a lithium atom at each end in an t/2-PP coordination mode [Li-P = 2.542(6) and 2.559(6) A]. The lithium atoms achieve four-coordination through the coordination of two molecules of THF each. Hydrolysis of this complex is an excellent route to the otherwise inaccessible tetraphosphine (Ph2P)2CHCH2 2, a potentially useful polyphosphine ligand analogous to two linked bis(diphenylphosphino)-methane (dppm) moieties. 

Fig. 16.7 Water-soluble polyphosphine metal catalysts used to hydrogenate thiophenes.

The solutions of alkali pentaphospholides MP5 are gold-orange to red in color and are extremely sensitive to oxidation. The pentaphospholide ion P5 reacts with alkyl halides RBr and RI. The alkyl pentaphospholes RP5 which are to be assumed as the primary products are non-aromatic and unstable, however, and rearrange to alkyl polyphosphines such as R3P7 and R3P9 <88AG288>. The trimethylsilyl pentaphosphole is known as a complex ligand (see Section 4.22.12.1.2). 

Dianions of the type [P R ] , which were first generated by reduction of cyclophosphines with two equivalents of alkali metals in TFIF, have chain structures. As such, they are potential synthons for the introduction of other elements into polyphosphine rings via metathesis reactions. More... 

Includes bibliographical references and indexes. Contents v. 1. Primary, secondary, and tertiary phosphines, polyphosphines, and heterocyclic organo-phosphorus(III) compounds—v. 2. Phosphine oxides, sulphides, selenides, and tellurides—v. 3. Phosphonium salts, ylides, and phosphoranes. 

Volume 1 covers primary, secondary and tertiary phosphines (PR3H3 , n= 1-3), polyphosphines (both P—(C) —P and R(P) R, n > 1) and heterocyclic compounds containing phosphorus. 

Five-coordination is now quite common in nickel(II) complexes and many polydentate ligands such as polyamines, salicylaldimines, polyarsines and polyphosphines have been designed with the purpose of favouring this stereochemistry.7,8 However, five-coordinate complexes with monodentate ligands ([Ni(CN)s]3 and [Ni(OAsMe)s]2+) are also known. 

The phosphorus macrocycles are made via template condensation of coordinated polyphosphine ligands and a dibromoalkane (equation 8).60 A more recently reported method involves a template-assisted single-stage ring closure (equation 9).61 The arsenic donor macrocycles are synthesized by reacting lithiated polyarsanes with a dichloroalkane (equation 10).62... 

Two general methods are available for preparing polyphosphines containing PCH2CH2P structural units and phosphorus-hydrogen bonds ... 

The product is the first example of a polyphosphine containing tertiary, secondary, and primary phosphorus atoms in the same molecule. 

Polyphosphines Containing Terminal Dialkylamino or Alkoxy Groups... 

---