Trifluoro phosphine

P. L. Timms, Chemistry of Transition-metal Vapours. Part I. Reactions with Trifluoro-phosphine and Related Compounds, J. Chem. Soc. A, 1970, 2526-2528. 

Other synthetic routes reported involve the interactions of trifluoro-phosphine metallates and iodine (method E), displacement of carbon monoxide, alkenes, etc. by PF3 from the corresponding halide complexes (method F), addition of PF3 to dinuclear halogeno-bridged PF3 complexes at low temperatures (method G), and treatment of a metal hydrido- PF3 complex with iodoform (method H). 

Direct addition of PF3 to 5-pentadienyl metal complexes offers an alternative synthetic route (method G) and this has been reported in the case of the formation of bis(2,4-dimethylpentadienyl)trifluoro-phosphine complexes of titanium and vanadium [M(C7H11)2PF3] (M = Ti, V) (Scheme 11) 111). 

Substitution of CO in the perfluoroalkyl metal carbonyl derivative provides a synthetic route to perfluoroalkyl mixed-carbonyl trifluoro-phosphine metal complexes (method D). 

A number of transition metals have been shown to react with trifluoro-phosphine [280]. Chromium, cobalt, nickel, palladium and iron all produced stable complexes. Manganese and copper also reacted at —196°C, but the products were unstable, and decomposed on warming. Nickel vapour has also been reacted with difluorochlorophosphine, yielding Ni(PF2Cl)2. Complexes produced by reaction with phosphine itself were unstable, decomposing on warming, although when a mixture of phosphine and trifluorophosphine was co-condensed with nickel vapour some mixed complexes were isolated. 

It must, however, be noted that the antibonding orbitals can be strongly stabilized by very electronegative substituents, as, for example, in trifluoro-phosphine, PF3. In such a case, these orbitals can interact to a non-negHgible extent with the i orbitals of the metal centre. This is particularly important for the 2e orbitals (Figure 1.4) which can be involved in Tr-type interactions (see Chapter 3). 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

The rate of solvolysis of the phosphinic chlorides (83a, b) in trifluoro-acetic acid and aqueous acetone (the composition of the latter solvent being chosen such that the rate of S nI solvolysis of Bu Cl was the same in both) have been examined to assess the possible operation of an 5 n1(P) ionization mechanism. In the more nucleophilic aqueous acetone solvent,... 

Bicyclo[2.2.1]hepta-2,5-diene-l,4-bis(diphenylphosphino)butanerhodium trifluoromethanesulfonate Rhodiura(l+), [(2,3,5,6- )-bicyclo[2.2.1]hepta-2,5-diene][l, 4-butanediylbi s[diphenyl phosphine]- ,P ]-, tri f1uoromethanesulfonate Bicyclo[2.2.l]hepta-2,5-diene-2,4-pentanedionatorhodiurn Rhodium, (2,5-norbornadiene) (2,4-pentanedionato)- (8) Rhodium, [(2,3,5,6- )-bicyclo[2.2.l]hepta-2,5-diene] (2,4-pentanedionato-0,0 )- (9) (32354-50-0) Trimethylsilyl trifluoromethanesulfonate Methanesulfonic acid, trifluoro-, trimethylsilyl ester (8,9) (27607-77-8)... 

The addition of phosphine to olefins is accelerated by acidic and basic catalysts. Under the influence of non-oxidising acids or Lewis acid such as, for example, methanesulphonic acid, benzenesulphonic acid, trifluoro-acetic acid or boron trifluoride phosphine is quickly added to olefins at pressures of 20-40 at, and temperatures of 30-60 °C. It is assumed that the reaction proceeds via a carbonium ion which is first formed thus ... 

A. frans-HYDRIDO(METHANOL)BIS(TRIETHYL-PHOSPHINE)PLATINUM(II) BIS(TRIFLUORO-METH ANESULFON ATE) (1 -)... 

Direct addition of VI to chlorocarbonylbis(phosphine)rhodium complexes containing more basic phosphine ligands to yield optically active complexes of the type III did not occur. An optically active benzylrho-dium complex (X) was obtained, however, by adding (S)a-trifluoro-methylbenzylchlorosulfite (IX) to chlorocarbonylbis (diethylphenylphos-... 

Phosphinate Diethyl Hexafluoro-4-(trifluoro-etlienyloxy)-propane EI0b2, 153 (-Cl2 -> En)... 

In related work, 3-chloromethylcephems were coupled with tributyI(trifluoro-vinyl)stannane catalyzed by tri(2-furyl)phosphine palladium(O) [7 , 79] (equation 13). 

Phosphine, seleno-metal complexes, 664 bidentate, 664 Phosphine, tributyl-, 992 Phosphine, trichloro-, 990 Phosphine, tricyclohexyl-, 992 Phosphine, triethyl-, 992 Phosphine, trifluoro-jt acidity, 1034 Phosphine, triisopropyl-, 992 Phosphine, trimethyl-, 990, 992 oxides... 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

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