Manganese complexes alkyl

Analogously, reaction of group 7 metal carbonyl anions M(CO)5 (M = Mn, Re) with MeC(CFFI), gave cyclopropylcarbinyl complexes. Flowever, whereas rhenium produces the normal (/-metal bonded cyclopropylcarbinyl complex, the manganese complex furnished (cyclopropylacetyl)Mn(CO)5, where carbonyl insertion into the manganese-alkyl bond occurred (equation 56)114. 

Isophorone can be cleanly oxidized by air to l,5,5-trimethylcyclohexene-3,6-dione in the presence of Mn(salen) and triethylamine (equation 2 1 4).524 The mechanism suggested involves carbanion (160) formation from the reaction of NEt3 with /3-isophorone, followed by the formation of an alkyl peroxide-manganese(III) complex (161) which decomposes to the dienone (162).524,56... 

Bis(alkyl) complexes, with mercury, preparation, 2, 428 Bis(alkylidene)s, in Ru and Os half-sandwiches, 6, 583 Bis(alkylimido) complexes, with chromium(VI), 5, 346 Bis(rj2-alkyne)platinum(0) complexes, preparation, 8, 640 Bis(alkynyl) complexes in [5+2+l + l]-cycloadditions, 10, 643 with manganese, 5, 819 with mercury, preparation, 2, 426 mononuclear Ru and Os compounds, 6, 409 with platinum, 12, 125 with platinum(II), 8, 539 with titanium(IV), 4, 643 with zirconium, 4, 722... 

Homoleptic germylenes, preparation and properties, 3, 773 Homoleptic lanthanide(II) alkyl compounds, properties, 4, 4 Homoleptic manganese aryl complexes, preparation, 5, 816 Homoleptic manganese isonitrilates, preparation, 5, 773—774 Homoleptic molybdenum complexes, preparation and characteristics, 5, 514... 

Asymmetric imidations of aryl alkyl sulfides with [(tosylimino)iodo]ben-zene, catalyzed by various chiral (salen)manganese(III) complexes, have been investigated in some detail [31,32]. The influence of catalyst structure, solvent, temperature, 3°-amine AT-oxides, and the presence of molecular sieves on product yields and the enantioselectivity of imidation with 17 was evaluated. Enan-tioselectivities as high as 90 % ee and 97 % ee with methyl 2-nitrophenyl sulfide and methyl 2,4-dinitrophenyl sulfide, respectively, were achieved. 

Compared to manganese, little work has been carried out on analogous alkyl complexes of rhenium, although that which has may be divided into the same categories, namely, (1) reaction with transition metal hydrides, for example [CpW(H)(CO>3] (2) reaction with Lewis acids, for example, AlCUEt (3) orthometallation reactions (4) reaction with cationic species, for example, (5) reaction with anionic nucleophiles, for example, BF4" (6) reaction with neutral nucleophiles, for example, PPh3-... 

R " = H, alkyl, aryl, substituted alkyl and aryl SIRs = SIMes, SiMe2(t-Bu), SIEts solvent CHoCH. pentane, toluene n = 1-3 chiral oxidant Davis chiral oxaziridine, Shi s D-fructose derived ketone/Oxone, (Salen)manganese(lll)-complexes/NaOCI or PhIO... 

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