Cyclooctene complexes manganese

The intermediate cw-cyclooctene complex can be prepared by the method of Fischer and Herberhold. Tricarbonyl(//-cyclopentadienyl)manganese(I)t... 

Finally it may be noted that N transfer from nitrido species such as salen or porphyrin complexes of manganese, e.g., porph Mnv=N, to organic substrates can occur. Examples are aziridation of cyclooctene or animation of silylenol ethers.167... 

Similar manganese porphyrin dimers linked by different spacer molecules had catalase activity [196]. The activity was highest when the Mn-Mn separation was ca 4 A, in agreement with the Mn-Mn separation in the hypothetical Mn -O-O-Mn complex [196]. The high-valent Mn porphyrin dimer has been prepared by the oxidation of the Mn dimer with wCPBA. The Mn dimer thus formed was stable for hours at temperatures ranging from —78 to -20 °C and it was detected by ESI MS (electrospray ionization mass spectroscopy) [197]. Cyclooctene was oxidized by mCPBA (1.1 equivalent for each Mn ion) with the Mn dimer to... 

QH P, Phosphine, dimethylphenyl-, iron complex, 26 61 molybdenum complex, 27 11 osmium complex, 27 27 osmium-rhodium complex, 27 29 osmium-zirconium complex, 27 27 ruthenium complex, 26 273 CkH,2, 1,5-Cyclooctadiene, iridium complex, 26 122, 27 23 osmium-rhodium complex, 27 29 ruthenium complexes, 26 69-72, 253-256 CbH 20,PS, 2-Butenedioic acid, 2-(dimeth-ylphosphinothioyl)-, dimethyl ester, manganese complex, 26 163 ChH,4, Cyclooctene, platinum complex,... 

A remarkable approach was reported in 2004 by Simormeaux and coworkers [53]. Manganese complexes of spirobifluorenyl-substituted porphyrins were elec-tropolymerized by anodic oxidation and the resulting poly(9,9 -spirobifluorene manganese porphyrin) films were shown to be efficient epoxidation catalysts in the presence of imidazole. The polymers were tested in the epoxidation of cyclooctene and styrene using PhIO or PhI(OAc)2 as oxidants. Epoxide yield reached 95% in the case of cyclooctene and 77% in the case of styrene. The electrosynthesized polymers could be recovered by filtration and reused up to eight times without loss of activity and selectivity. 

The electrophilic 0x0 of the Hangman platform is also susceptible to nucleophilic attack by the two-electron bond of olefins. The reaction parallels the peroxide shunt cycle (198-200) of cytochrome P450 and peroxidase enzymes while building on the results of the observed biomimetic catalase activity. The common olefins styrene and c/i-cyclooctene were chosen as substrates for epoxidation by the manganese HPX and HPD derivatives MnCKHPX-COaH) (33), The MnCl(HPX-C02Me) complex (34) and MnCl(HPD—CO2H) (35) with MnCl(TMP) as the standard baseline compound. 

CgH,204PS, 2-Butenedioic acid, 2-(di-methylphosphinothioyl)-, dimethyl ester, manganese complex, 26 163 C,H,4, Cyclooctene, iridium and rhodium complexes, 28 90,91 platinum complex, 26 139 C,H,N, Benzene, 2-isocyano-13-dimethyl-, iron complexes, 26 53, 57,28 180-184 C9H )N, Benzenemethanamine,IVJV-... 

As seen from Table I, the heats of formation (AH2) of the Mn-SBu2 bond and the Mn-cw-cyclooctene bond were found respectively, to be -29.1 2.0 and -24.5 2.3 kcal/mol. Thus, we expected the Mn-SBu2 bond to be 4.6 3.0 kcal/mol stronger than the Mn-c -cyclooctene bond. To confirm this prediction, we examined the equilibrium shown below between the corresponding manganese complexes. 

---