Molybdenum complexes carbonylation

Molybdenum, tris(phenylenedithio)-structure, 1,63 Molybdenum alkoxides physical properties, 2,346 synthesis, 2,339 Molybdenum blue liquid-liquid extraction, 1,548 Molybdenum cofactor, 6,657 Molybdenum complexes acrylonitrile, 2,263 alkoxides, 3,1307 alkoxy carbonyl reactions, 2,355 alkyl, 3,1307 alkyl alkoxy reactions, 2,358 alkyl peroxides oxidation catalyses, 6,342 allyl, 3,1306... 

Casares, J.A., Espinet, P., Hernando, R., Iturbe, G., Villafane, F., Ellis, D.D. and Orpen, A.G. (1997) Poly(2-pyridyl) phosphines, PPynPh3 (n = 2, 3), and Their P-Substituted Derivatives as Tripodal Ligands in Molybdenum(O) Carbonyl Complexes. Inorganic Chemistry, 36(1), 44-49. 

Alkylidene carbonyl iridium complexes, reactions, 7, 275 Alkylidene compounds, NLO properties, 12, 121 Alkylidene-containing complexes, in molybdenum complexes, Schrock-type complexes, 5, 524 a-Alkylidene cyclic carbonyl compounds, isomerization,... 

Susuki and Tsuji reported the first Kharasch addition/carbonylation sequences to synthesize halogenated acid chlorides from olefins, carbon tetrachloride, and carbon monoxide catalyzed by [CpFe(CO)2]2 [101]. Its activity is comparable to or better than that of the corresponding molybdenum complex (see Part 1, Sect. 7). Davis and coworkers determined later that the reaction does not involve homolysis of the dimer to a metal-centered radical, which reduces the organic halide, but that radical generation occurs from the dimeric catalyst after initial dissociation of a CO ligand and subsequent SET [102]. The reaction proceeds otherwise as a typical metal-catalyzed atom transfer process (cf. Part 1, Fig. 37, Part 2, Fig. 7). 

Electrocyclization of E is expected to give cyclohexadienone complex F a related molybdenum complex 6 (Scheme 4), in which two carbonyl ligands have been replaced by alkyne ligands, has been isolated from the reaction of a vinyl molybdenum carbene complex with 3-... 

Liberation of the 1,4-dihydrophosphinines 76a,b thus synthesized is accomplished by heating carbonyl molybdenum complexes 75a,b in the pres-... 

Similarly, orange-red needles (mp 53 °C) of 1-fluoroborepin molybdenum carbonyl complex 18 were obtained by conversion of 1-methoxyborepin 17 to the corresponding Mo(CO)3 complex followed by immediate treatment of the crude complex with boron trifluoride in pentane, as in Scheme 1. The intermediate molybdenum complex of 17 could be isolated as air- and moisture-sensitive crystals (mp 110-115 °C) but prolonged manipulation led to contamination by the corresponding 1-hydroxyborepin complex <19970M1884>. 

Although bis(phosphite) carbyne complex Cp[P(OMe)3]2Mo=C(c-Pr) is incapable of undergoing carbonyl insertion reactions, it adds 1 equivalent of HCl in ether forming the ring-opened f/ -butadiene complex Cp[P(OMe)3](Cl)Mo( / -butadiene) in 15% yield, and P(OMe)3 in equal amounts (equation 108) . Careful analysis of the reaction using two equivalents of HCl reveals the presence of the metal hydride complex Cp[P(OMe)3]2Cl2MoH as the main products (70%), and free butadiene. It was furthermore shown that the two molybdenum complexes are not interconvertible under the reaction conditions and both the yields and products ratio are invariant with temperature in the range of -40 °C to room temperature and the amount of added HCl (1 or 2 equivalents). 

Cyclohexadiene-Mo(CO)iCp complexes. The molybdenum complex 1 is prepared from 3-bromo-1-cyclohexene by reaction with molybdenum carbonyl and lithium cyclo-pentadienide followed by hydride abstraction. It undergoes a highly regio- and stereoselective reaction with a Grignard reagent to gi c an adduct (2) with an axial substituent... 

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