2- diphenylphosphine, reaction with

P-phosphino-NHPs but the reverse reaction of a P-chloro NHP with diphenyl-trimethylsilylphosphine and subsequent reaction with a chloroalkane can be combined to produce high yields of P-alkyl-diphenylphosphines [74], Since the chloro-NHP is recovered in the second step, the overall reaction can be performed by employing this species merely as catalyst (Scheme 13). NMR investigations confirm that the appropriate P-phosphino-NHPs are in fact key intermediates in the resulting catalytic cycle, and it has been pointed out that P-X bond polarization represents a crucial factor for the overall acceleration of the catalyzed P-C... 

Reaction of 1,2-propadienyl diphenylphosphine oxide and MX (M = Na, Li, X= Cl, Br, I) in HOAc leads to 2-halo-2-propenyl diphenylphosphine oxides in 58-75% yields. With substituent(s) in the allene moiety, the reaction is very slow. The corresponding reaction with HX gives low yields [87]. 

The mixed triarylphosphine 787 can be prepared by the reaction of (trimethylsilyl)diphenylphosphine (786) with aryl halides[647]. Ph3P is converted into the alkenylphosphonium salt 788 by the reaction of alkenyl tri-flates[648]. 

Several mixed-metal clusters containing platinum and cobalt are known and some of them have been employed as methanol homologation catalysts.1 Among them, the title compound2 was first prepared unambiguously from the reaction of dichloro[l,2-ethanediylbis(diphenylphosphine)]platinum with sodium tetracarbonylcobaltate, Na[CO(CO)4]. The compound also may be prepared by the reaction of [l,2-ethanediylbis(diphenyl-phosphine)]bis(phenylethynyl)pIatinum with Co COJg.1... 

Platinum(II)15 and palladium(II)16 complexes of phosphorus trichloride undergo solvolysis in water and alcohols to form complexes with orthophosphorous acid or orthophosphite ligands (equation 6). Similar reactions occur between the palladium(II) phenyldichlorophosphine complex (8) and the diols ethyleneglycol and catechol, but new chelate rings are not formed (Scheme 2). Solvolysis also occurs with attack of diphenylphosphinic acid or a similar diphenylchlorophosphine complex (9) (equation 7). The palladium complexes (8) and (9) are unstable to excess methanol, water or base and undergo reduction. Similarly, the phosphorus trichloride gold(I) complex (10) is reduced by water, but forms stable products on reaction with alcohols (equation 8).15 During the above reactions, the phosphorus—metal bond remains intact and the overall process is one of substitution at phosphorus. 

Methyl-metal bond cleavage also occurred in the reactions of gold(I), gold(III), and platinum(II) compounds with thiols and selenols (207-209). The reactions of gold(I) and platinum(II) complexes were much faster than those of gold(III), due to the operation of a radical chain mechanism in the former cases. For the reactions with diphenylphosphine, however, the following order of reactivity was found (209) ... 

The coupling reaction of diphenylphosphine sulfide with A,A-disubstituted for-mamides in the presence of an excess of sodium hydride resulted in the corresponding aminomethyldiphenylphosphine sulfides in good yields. It is suggested that the carbon-oxygen bond is cleaved by sodium hydride (Scheme 12)308... 

So far as we know, this approach has been used only once, although it should be capable of extension. The octahedrally coordinated rhodiacyclopentadiene complex 94, which results from the reaction of [RhCl(PPh3)3] with 2 mol of (2-phenyl-ethynyl)diphenylphosphine, reacts with diphenylacetylene to give the di-strapped arene-rhodium(I) complex 95, from which the p-terphenyl-based bis (diphenylphosphine) can be released by heating with NaCN [Eq. (19)].84... 

Technetium(V) complexes with /u,v(ohydroxyphenyl)phenylphosphine and (o-hydroxyphenyl)diphenylphosphine ligands were prepared by metathesis reactions with the appropriate Tc(V) precursor and/or by reduction/ligand-exchange reactions with ammonium pertechnetate [530]. It was expected that the combination of one soft phosphine P-donor and two hard phenolate O-donors in the chelate should stabilize Tc centers in intermediate oxidation states. 

Dimethylindole readily forms phosphines 26 and 3-(l,2-dimethylindolyl)diphenylphosphine 27 in reaction with phosphorus tribromide or diphenylchlorophosphine in the presence of triethylamine. The formed phosphines without isolation from the reaction mixture are transformed into derivatives containing tetracoordinated phosphorus atom 28 [28],... 

The reaction with diphenylphosphine or diethylphosphine provides a synthetic pathway leading to the diaminophosphinocyclopropenium compound 30). Both the characteristic bands (A,B) indicate the existence of the cyclopropenyl ring (Eq. (16)). 

Diphenyltrifluorophosphorane was first obtained by the reaction of diphenylphosphinic acid with sulfur (IV) fluoride under autogenous pressure. The present method consists in the reaction of diphenylchlorophosphine with arsenic(III) fluoride at atmospheric pressure. ... 

It should be noted that the reactions described above cannot be performed in the reverse order, i.e., preparation of the chlorophosphine followed by reaction with LiAsPhz. The reaction of lithium diphenylphosphine with cfr-l,2-dichloroethylene, even with a large excess of the latter, yields only cw-l,2-bisdiphenylphosphinoethylene and not the chlorophosphine, and while 2-chloroethyldiphenylphosphine can be prepared, its isolation is more difficult, and yields are lower than for the corresponding arsine. ... 

Boiling a solution of (2,2-dimethylhydrazino)diphenyl-phosphine in benzene overnight in contact with dry air causes precipitation of the oxide, (C8H5)2P(0)NHN(CH3)2 (m.p. 167 to 168°). Addition of a stoichiometric amount of sulfur to a boiling benzene solution of (2,2-dimethylhydrazino) diphenylphosphine yields, on cooling, the sulfide, (C H5)2P(S)NHN(CH3)2 (m.p. 95.5 to 97.0°). Alkylation to [(C6H5)2(CH3)PNHN(CH3)2]I (m.p. 156 to 158°) occurs upon reaction with methyl iodide in ether. Reaction with chloramine in ether yields the aminophosphonivun salt, [(C,H,)2P(NH2)NHN(CH,)2]C1 (m.p. 195°). All of the above-described derivatives are colorless solids. 

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