Manganese complexes amides

In the IR spectra (table 2) of the encapsulated manganese complexes amide-bands are the dominating spectral features, just as for the free complexes. Evidence for one or another way of coordination comes from the analysis of the amide modes. The amide I bands, attributed to CO-absorption bands in the range 1650-1630 cm for secondary amides, are visible for most of the Mn(bpR)-Y samples. The amide II band is a combination of C-N stretch and C-N-H bending. 

Chiral manganese complexes have been used to perform the enantioselective amidation of saturated C-H bonds.256-258,262 Cationic Mn(salen) 107 showed good catalytic activity and moderate enantioselectivity. Typical examples are shown in Equations (86)-(88). High enantioselectivity of 89% ee was obtained in the reaction of 1,1-dimethylindan (Equation (88)).258 Chiral manganese(m) porphyrin 106 was used in the enantioselective amidation as well nevertheless, the best enantioselectivity was only 54% (Equation (89)).256,257... 

The amidation of saturated C—H bonds can be effectively catalyzed by ruthenium or manganese complexes. Unfunctionalized hydrocarbons, such as adamantane, cyclohexene, ethylbenzene, cumene, indane, tetralin, diphenylmethane and others, are selectively amidated with PhINTs in the presence of ruthenium or manganese porphyrins or the ruthenium cyclic amine complexes to afford N-substituted sulfonamides in 80-93% yields with high selectivity [807]. The enantioselective amidation of a C—H bond can be catalyzed by chiral (salen)manganese(III) complexes (e.g., 660) [808], or by chiral ruthenium(II) and manganese(III) porphyrins (Scheme 3.264) [809]. 

Aryl alkyl ketones (e.g. 161) can be converted to amides (e.g. 162), with a loss of the alkyl group, by reaction with a carbodiimide. This unusual C -C arbonyi single-bond cleavage is catalysed by manganese complexes such as [HMn(CO)4l3 or Mn2(CO)io-Aryl isocyanates, Ar-N=C=0, are mechanistically implicated, as the reaction can also be carried out using such isocyanates, and indeed, two isocyanate molecules can be converted to the corresponding carbodiimide using either catalyst. ... 

An asymmetric C-H insertion using a chiral 3,3, 5,5 -tetrabromosubstituted (salen)manganese(m) complex 107 with TsN=IPh afforded insertion products with ee up to 89%.258 Che reported the first amidation of steroids such as cholesteryl acetate with (salen)ruthenium(n) complexes 108.259... 

In company with manganese porphyrin complex, ruthenium porphyrins have already shown great catalytic activity in the intermolecular amidation of saturated G-H bonds. However, examples of amidation of aromatic... 

Complexes. N- )o/ior Ligands. The reaction of manganese and the respective alkali metal in liquid ammonia yields the amide complexes M2Mn(NH2)4 (M = Na, K, Rb, or Cs). °... 

The stability constant (7=0.1, 25 °C) has been reported for the 1 1 manganese(II) complex of the related amide-containing, 15-membered macrocycle l,4,7-trimethylcarboxy-9,14-dioxo-1,4,7,10,13-pentaazacyclopentadecane as 14.7 (log value). ... 

Like carbene insertions into carbon-hydrogen bonds, metal nitrene insertions occur in both intermolecular and intramolecular reactions.For intermole-cular reactions, a manganese(III) meio-tetrakis(pentafluorophenyl)porphyrm complex gives high product yields and turnovers up to 2600 amidations could be effected directly with amides using PhI(OAc)2 (Eq. 51). The most exciting development in intramolecular C—H reactions thus far has been the oxidative cychzation of sulfamate esters (e.g., Eq. 52), as well as carbamates (to oxazolidin-2-ones), ° and one can expect further developments that are of synthetic... 

Manganese(tl) complexes,, 3, 9-82 acctylacetonates, 48 acetylides, 14 alcohols, 37 alkoxides, 37 alkyl phosphines, 13 alkyls, 12 amides, 15, 16 amine oxides, 39 amines, 16 amino acids, 43, 62 sulfur containing, 70 ammines, 15 antimony ligands, 31-34 arsenates, 4,5, 46 arsenic ligands, 31-34 arsenic oxides, 39 aryls, 12, 14 azides, 22 binary alkyls, 13 bipyridyl, 24, 25 anions, 25... 

---