Phosphines, metalation

Bromine Ammonia, carbides, dimethylformamide, fluorine, ozone, oleflns, reducing materials including many metals, phosphine, silver azide... 

Bergmann D, Hinze J (1987) Electronegativity and Charge Distribution. 66 145-190 Berners-Price SJ, Sadler PJ (1988) Phosphines and Metal Phosphine Complexes Relationship of Chemistry to Anticancer and Other Biological Activity. 70 27-102 Bertini I, see Banci L (1990) 72 113-136... 

Brown JM, Chalnoer PA (1983) In Pignolet NH (ed) Homogeneous catalysis with metal phosphine complexes. Plenum, New York, chap 4... 

Pignolel. 1.. H. Homogeneous Catalysis with Metal Phosphine Complexes Plenum New York. 

Pyrophoric carbonyl metals Phosphine Tri butyl phosphine ... 

B. From Metallated Phosphines.—Lithium diphenylphosphide and ethylene oxide produce (7), which when added to chlorodibutyl- or chlorodiphenyl-phosphine yields 2-diphenylphosphinoethyl phosphinites (8). 

A catalytic cycle proposed for the metal-phosphine complexes involves the oxidative addition of borane to a low-valent metal yielding a boryl complex (35), the coordination of alkene to the vacant orbital of the metal or by displacing a phosphine ligand (35 —> 36) leads to the insertion of the double bond into the M-H bond (36 —> 37) and finally the reductive elimination to afford a hydroboration product (Scheme 1-11) [1]. A variety of transition metal-boryl complexes have been synthesized via oxidative addition of the B-H bond to low-valent metals to investigate their role in cat-... 

Scheme 1-11 Catalytic Cycle for Metal-Phosphine Complexes...

Although a wide variety of metals were claimed as active catalysts for formaldehyde hydrophosphination, platinum salts were preferred. Similarly, Group 10 metal salts were used to catalyze acrylonitrile hydrophosphination. Russian workers showed that Ni(II) or Co(II) salts in the presence of ammonia or amines would also catalyze the addition of phosphine to formaldehyde [6]. More recently, academic and industrial interest in these reactions was sparked by a series of papers by Pringle, who investigated late metal phosphine complexes as hydrophosphination catalysts. These and related studies are arranged below by substrate. 

Preparation of Phosphines from Metallated Phosphines.- It has been shown that phosphide anions may be generated from primary and secondary phosphines under aqueous conditions using concentrated aqueous alkali in DMSO or other dipolar aprotic solvents. 

A potentially interesting development is the microwave-assisted transition-metal-free Sonogashira-type coupling reaction (Eq. 4.10). The reactions were performed in water without the use of copper(I) or a transition metal-phosphine complex. A variety of different aryl and hetero-aryl halides were reactive in water.25a The amount of palladium or copper present in the reaction system was determined to be less than 1 ppm by AAS-MS technique. However, in view of the recent reassessment of a similarly claimed transition-metal-free Suzuki-type coupling reaction, the possibility of a sub-ppm level of palladium contaminants found in commercially available sodium carbonate needs to be ruled out by a more sensitive analytical method.25 ... 

Complexes with mixed C,P or C,As donor ligands are derived of ortho-metalated phosphines or arsines or of methanide derivatives. The dinuclear complexes [Au2(C6F[3-2-EPh2-6-R)2] (E = P (589), As R = H, Me) are obtained by reaction of 2-EPh2-6-R-C6F[3Li with [AuBr(PEt3)] at —70 °c.2002 2004,20 6 The treatment of the dimer [Au2(C6Fl4PPh2)2] with methyltriflate yields, unexpectedly, [Au5(C6Fl4PPh2)4]+.3134 The mixed dinuclear derivative [Au2(5-Me-C6H3-2-... 

Scheme 2. Air-stable coupling catalysts derived from combinatorial approaches expectedly coordinated to the metal centers through phosphorus atoms to form metal-phosphinous acid compounds [Scheme 2].2,3...

Potassium chlorate See Potassium chlorate Reducants See Other METAL PHOSPHINATES, REDUCANTS... 

See Other HEAVY METAL DERIVATIVES, METAL PHOSPHINATES, REDUCANTS 4520. Hydrazine... 

See other heavy metal derivatives, metal phosphinates, reducants... 

The salt evolves spontaneously flammable phosphine around 240°C. See other reducants See related metal phosphinates... 

A variety of Group VIII transition metal phosphine complexes are shown to be active catalysts for hydrogenation of aliphatic nitro compounds. However, chiral phosphines have been found to be noneffective to induce asymmetric induction.110... 

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