Reaction Of Tertiary Phosphines Research Articles

Metal nitrido- and oxo-complexes. Part II. Osmium and ruthenium nitrido-complexes with Group 5 ligands and their reactions

Reactions of Y[Os(N)X4] and Y[Ru(N)Cl4](Y = Ph4As or Bun4N; X = Cl or Br) with arsines, stibines, and 2,2′-bipyridyl (bipy) give the nitrido-complexes [Os(N)X3L2] and [Ru(N)Cl3(QPh3)2](L = QPh3, AsEt3, or ½bipy; Q = As or Sb), but tertiary phosphines give reduced species. Reaction of tertiary phosphines with [M(N)Cl3(AsPh3)2](M = Os or Ru) give the phosphine imidato-complexes [M(NPR3)Cl3(PR3)2](PR3= PPh3, PPh2Et, PPhEt2, PEt3, or PPh2Me), and with dimethylphenylphosphine the intermediates [M(NPPhMe2)Cl3(AsPh3)2] have been isolated. Using [Os(N)Br3(AsPh3)2] the complexes [Os(NPR3)Br3(PR3)2](PR3= PPh3, PPh2Et, or PPhEt2) were obtained. Oxidation of [Os(NPR3)Cl3(PR3)2] by chlorine gave the nitrides [Os(N)Cl3(PR3)2]. Other new complexes which have been obtained are [Os(NHPPh3)Cl4(PPh3)], [Ph4As][OsCl4(PPh3)2], [OsCl4(PPh3)2], [Ph4As][OsCl5(PPh3)], and [Os(OMe)2Cl2(PPh3)2]. The formation and reactions of these complexes are discussed.

The reaction of tertiary phosphines with tropylium chromium tricarbonyl tetrafluoroborate

The reaction of tertiary phosphines with tropylium chromium tricarbonyl tetrafluoroborate

Carbon phosphorus bond cleavage in the reaction of tertiary phosphines with boron trihalides

Carbon phosphorus bond cleavage in the reaction of tertiary phosphines with boron trihalides

Reaction of tertiary phosphines with dichloramines

Reaction of tertiary phosphines with dichloramines

New cobalt(I) complexes derived from dicarbonyltricyanocobaltate(I)

The preparation and characterization of several series of mixed ligand cobalt(I) complexes of the types [Co(CN)2(CO)2(PR3)]–, [Co(CN)2(CO)(PR3)2]–, and [Co(CN)(CO)2(PR3)2], prepared by the reactions of tertiary phosphines (PR3) with [Co(CN)3(CO)2]2–, are described and some novel aspects of their chemistry are discussed.

Reactions of phosphines with acetylenes. Part IX. 1,2-Alkylidenediphosphoranes stabilised by acyl and ester groups

1,2-Alkylidenediphosphoranes stabilised by acyl groups have been prepared quantitatively from the reaction of tertiary phosphines (2 mol.) and diacylacetylenes (1 mol.). The phosphoranes are thermally less stable and more readily hydrolysed than the corresponding phosphoranes stabilised by ester groups. The hydrolyses occur with expulsion of tertiary phosphine and the driving force for the fragmentation is shown not to be derived from the donation of electrons by a phosphoranyl group but probably from the formation of a PO bond. The diphosphorane derived from diphenylmethylphosphine and dimethyl acetylenedicarboxylate has been synthesised by an alternative route.

Reaction of tertiary phosphines with hexafluoroacetone and with o-quinones. Attack by phosphorus on carbonyl oxygen and isolation of 2,2,2-trialkyl-2,2-dihydro-1,3,2-dioxaphospholanes

Reaction of tertiary phosphines with hexafluoroacetone and with o-quinones. Attack by phosphorus on carbonyl oxygen and isolation of 2,2,2-trialkyl-2,2-dihydro-1,3,2-dioxaphospholanes

Compounds with pentavalent phosphorus and with tetravalent phosphorus from the reactions of trivalent phosphorus compounds with α,β-unsaturated ketones : Dipolar ions from the reactions of tertiary phosphines with 3-benzylidene-2,4-pentanedione

The phosphorus of trialkyl phosphines, R 3P, and dialkylarylphosphines, R 2PhP, added to the β-carbon of the α,β-unsaturated ketone, 3-benzylidine-2,4-pentanedione. The crystalline 1:1 adducts had the structure of open dipolar with tetravalent phosphorus. These gave negative 31P NMR shifts relative to H 3PO 4. The 1:1 adducts from the reactions of the same unsaturated ketone with phosphite, phosphonite, and phosphinite esters, (RO) 3P, (RO) 2PhP, (RO)Ph 2P, had the structure of 5-membered cyclic oxyphosphoranes with pentavalent phosphorus. These gave positive 31P NMR shifts. These differences are attributed mainly to the higher electronegativity of oxygen than of carbon, which tends to favor the pentacovalent state of the phosphorus. The operation of steric effects is indicated by the relative instability of the adducts made from dialkylaryl-phosphines and triaryl phosphines, which tend to dissociate into the tertiary phosphine and the unsaturated ketone.

Trialkyl- and triaryl-alkylidenephosphoranes from the reaction of tertiary phosphines with trans-dibenzoylethylene

Trialkyl- and triaryl-alkylidenephosphoranes from the reaction of tertiary phosphines with trans-dibenzoylethylene