Manganese nitrosyls

Manganese nitrosyl porphyrins [215] are considered good models for the iron-nitric oxide analogs, which are relatively unstable but very vital to many biological operations. A six-coordinate manganese nitrosyl porphyrin of the form (por)Mn(NO)(L), where por can be TTP (TTP = tetra(4-methylphenyl)porphine) and L = piperidine, methanol, 1-methyhmidazole, has been prepared [216] in moderate yields by the reductive nitrosylation of the (por)MnCl complex with NO in piperidine. The crystal structures of these compounds give indication of a linear Mn-NO bond [215]. 

Manganese-gallium bonds, formation, 5, 764-765 Manganese isonitriles, synthesis and characteristics, 5, 773 Manganese-nitrogen bonds, in Mn carbonyls, 5, 766 Manganese nitrosyl complexes, synthesis and characteristics, 5, 773... 

Hoffinan-Luca CG, Eroy-Reveles AA et al (2009) Syntheses, structures, and photochemistry of manganese nitrosyls derived from designed Schiff base ligands potential NO donors that can be activated by near-infrared light Inorg Chem 48 9104-9111... 

Ghosh K, Eroy-Reveles AA et al (2004) Reactions of NO with Mn (II) and Mn (III) centers coordinated to carboxamido nitrogen synthesis of a manganese nitrosyl with photolabile NO. Inorg Chem 43 2988-2997... 

Heilman BJ, Halpenny GM, Mascharak PK. Synthesis, characterization, and light-controlled antibiotic application of a composite material derived from polyurethane and silica xerogel with embedded photoactive manganese nitrosyl. J Biomed Mater Res B Appl Biomater 2011 99B 328-37. http //dx.doi.Org/10.1002/jbm.b.31904. 

A. A. Eroy-Reveles, Y. Leung and P. K. Mascharak. Release of nitric oxide from a sol-gel hybrid material containing a photoactive manganese nitrosyl upon illumination with visible hght. J. Am. Chem. Soc. 128, 2006, 7166-7167. 

Complexes of manganese with the 1,1-dithiolates have been restricted to the (PrSN)3[Mn(i-mnt)3] complex (112) and nitrosyl or carbonyl derivatives, e.g., [7i--CpMn(NO)(S2C==X)] (X = C(CN)C02Et, C(CN)C0NH2, NCN, C(CN)2, or (HNO2) (110, 204, 205). These complexes undergo electrochemical, one-electron oxidations and reductions to afford the neutral or dianionic species. 

Neutral (cyclohexadienyl)manganese complexes 71, generated by nucleophilic addition to (arene)Mn(CO)3+ cations 65, undergo ligand substitution with nitrosyl hexafluorophosphate to give the corresponding (cyclohexadienyl)Mn(CO)2NO+ cations 72 (Scheme 17)93. Attack by a wide variety of nucleophiles on cations 72... 

As has been deseribed, the parent monoearbollide-metal earbonyl piano-stool species [2-(CO) -c/oi o-2,l-MCBioHii] are now known for all of the metals M = Mo (12), W (13), Re (14), Fe (11), Ru (6), Os (8), and Ni (18). Evidence also exists for a diearbonyl-platinum analogue of eompound 18, ° and as mentioned earlier, the manganese analogue of 14 has also briefly been reported. A notable absenee from this list, however, is any representative of the Group 9 metals. The earbonyl nitrosyl-cobalt complex 21 is very elosely related to the hitherto unknown dicarbonyl-cobalt dianion [2,2-(CO)2-c/oi o-2,l-CoCBioHii] and this species remains an attractive synthetie target. 

Nitrosyl compounds of copper, manganese, iron, cobalt, nickel, and palladium... 

Nitrosyl-aryl porphyrin complexes, with iron, 6, 107 Nitrosyl complexes with chromium, 5, 301 with manganese, 5, 773... 

In the manganese compounds 7 the ester group seems to be more reactive than the nitrosyl group and the nucleophilic attack proceeds at the carbon atom with retention of configuration7,8 Therefore, for molecules of type 7 and 10 the reactivity sequence toward nucleophilic attack is2S 27 ... 

Dipole moment measurements, first carried out in our Munich Institute by E. Weiss (108), provided evidence of the very slight polar character of the metal-CO and metal-NO bonds. Similar measurements supplied information about stereochemistry for example, of cw-I2Fe(CO)4 (108), (Ph3P)3Fe(CO)2 (51), and [Fe(CO)3SEt]2 (90), as well as of the phosphine-containing nitrosyl carbonyl manganese compounds (105). 

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