51320-29-7Relevant academic research and scientific papers
Kinetics and Machanisms of Substitution Reactions on Decacarbonylmanganeserhenium
Sonnenberger, Dave,Atwood, Jim D.
, p. 3484 - 3489 (1980)
The kinetics of substitution reactions on decacarbonylmanganeserhenium, MnRe(CO)10, are reported for the entering ligands P(C6H5)3, P(C4H9)3, and P(OC6H5)3.Synthesis of all products and careful infrared analysis have allowed complete product assignment.For all three ligands the rhenium-substituted product, (CO)5MnRe(CO)4L, predominates, although formation of the bis-substituted product, L(CO)4MnRe(CO)4L, can be quite significant depending on the reaction conditions.A very small amount of the manganese isomer, L(CO)4MnRe(CO)5, was formed early in the reaction.In no cases were the homodimetallic species (Mn2(CO)10 or Re2(CO)10) or substituted derivatives of the diatomics observed.The manganese isomer fails to rearrange to the rhenium isomer under the conditions of the kinetics reaction.The rate constants and activation parameters are nearly identical for the three ligands.These data strongly suggest that CO dissiciation is the rate-determining step and are inconsistent with cleavage of the manganese-rhenium bond.Our proposed mechanism involves CO dissosiation from the manganese center and an intermediate/transition state with carbon monoxide bridging the manganese and rhenium.
Metallorganische Lewis-Saeuren. XXXVII. Kationische Pentacarbonyl(phosphan)rhenium-komplexe und deren Reactionen mit Nucleophilen
Steil, Peter,Sacher, Wolfgang,Fritz, Peter M.,Beck, Wolfgang
, p. 363 - 374 (2007/10/02)
The raections of pentacarbonyltetrafluoroboratorhenium, (OC)5ReFBF3, with PH3, PPh3, PPh2H, and chlorphosphanes lead to cationic complexes +BF4- (1).Nucleophiles react with the chlorphosphane ligands of 1 to give the ionic complexes +BF4- (R'=OH, OMe, OEt).Reaction of +BF4- with OH- yields the bridged 2+2BF4-, whereas with +BF4- and OH- the complex +BF4- is formed.The azide ion is added to a cis-carbonyl ligand of +BF4- to form the neutral isocyanato complex (OC)4(ClPh2P)ReNCO.The hydroxycarbonyl complexes cis-(OC)4Re(PPh2R)(COOH) are obtained from the reaction of +BF4- (R=Ph, H) with hydroxide.The reactions of + with M(CO)5- (L=PPh3, P(OMe)3, CN-tBu; M=Mn, Re) give the nonacarbonyl dimetal compounds L(OC)4Re-M(CO)5.
Intermolecular formation of C-H bonds: Application to the synthesis of heterobimetallic complexes
Warner, Keith E.,Norton, Jack R.
, p. 2150 - 2160 (2008/10/08)
The reactions of various alkylmetal carbonyl complexes (e.g., MeMn(CO)5, EtRe(CO)5, MeFe(CO)2Cp, Me2Os(CO)4) with various transition-metal hydrides (e.g., HRe(CO)5, H2Os(CO)4, HMn(CO)5, HW(CO)3Cp) have been examined in solvents of different coordinating abilities. In coordinating solvents the metal-containing products are solvated dinuclear complexes; in noncoordinating solvents the metal-containing products are polynuclear hydrides, formed by the coordination of a second equivalent of the hydride reactant. The vacant coordination site is created on the metal that originally bears the alkyl ligand: in CH3CN, MeMn(CO)5 and HRe(CO)5 give (CH3CN)Mn(CO)4Re(CO)5, whereas EtRe(CO)5 and HMn(CO)5 give (CH3CN)Re(CO)4Mn(CO)5. The organic products eliminated are generally aldehydes (although alkane elimination is also seen, particularly when the initial alkyl carbonyl complex is a dialkyl). The reaction is fastest in coordinating solvents and for the alkyl carbonyl complexes that most readily form acyls: MeMn(CO)5 and those complexes of other metals (e.g., EtRe(CO)5) that contain alkyl groups that migrate more readily than methyl. When heated in acetonitrile solution, EtRe(CO)5, i-BuRe(CO)5, and some other alkyl carbonyl complexes equilibrate with solvated acyl complexes such as cis-RC(O)(CH3CN)Re(CO)4; these solvated acyl complexes react rapidly at low temperatures with hydrides to eliminate aldehydes. In favorable cases, the reactions of alkyl carbonyls with transition-metal hydrides are synthetically attractive routes to heterobimetallic complexes.
