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{{expert-subject|date=December 2010}}
{{synthesis|date=December 2010}}
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[[Image:Ferrate ion.svg|thumb|right|ferrate ion [FeO<sub>4</sub>]<sup>2-</sup>]]
'''High-valent [[iron]]''' commonly denotes compounds and intermediates in which iron is found in a formal [[oxidation state]] > 3 that show a [[Valence (chemistry)|number of bonds]] > 6 with a [[coordination number]] ≤ 6. The term is rather uncommon for hepta-coordinate compounds of iron.<ref>Craig et al. Dalton Trans., 2010, 39, 4874-4881 {{DOI|10.1039/B927032A}}</ref> It has to be distinguished from the terms [[Hypervalent molecule|hypervalent and hypercoordinate]], as high-valent iron compounds neither necessarily violate the [[18-electron rule]] nor necessarily show coordination numers > 6. The [[ferrate]] ion [FeO<sub>4</sub>]<sup>2-</sup> was the first structure in this class synthesized. The synthetic compounds discussed below contain highly oxidized iron in general, as the concepts are closely related.
 
==Oxoiron compounds<ref>'''Review''': Que et al.; Journal of Inorganic Biochemistry Volume 100, Issue 4, April 2006, Pages 421-433;{{DOI|10.1016/j.jinorgbio.2006.01.014}}</ref>==
Oxoferryl species are commonly proposed as intermediates in [[catalytic cycles]], especially biological systems in which O<sub>2</sub> activation is required.  Diatomic oxygen has a high reduction potential (E<sup>0</sup> = 1.23 V), but the first step required to harness this potential is a thermodynamically unfavorable one electron reduction E<sup>0</sup> = -0.16 V.  This reduction occurs in nature by the formation of a [[superoxide]] complex in which a reduced metal is oxidized by O<sub>2</sub>The product of this reaction is a peroxide radical that is more readily reactive.  The abundance of these species in nature and the chemistry that is available to them are the reasons why the study of these compounds is important.{{Citation needed|date=December 2010}} A widely applicable method for the generation of high-valent oxoferryl species is the oxidation with [[iodosobenzene]].
:<math>\mathrm{(L)Fe^{n} + OIPh \longrightarrow (L)Fe^{n+2}O + IPh}</math>
:<small>symbolic oxidation of an iron compound using [[iodosobenzene]], L denotes the supporting ligand </small>
 
===Fe(IV)O===
[[Image:Fe4TMCSOPF6.png|thumb|120px|right|thiolate-ligated oxoiron(IV)]]
Several syntheses of oxoiron(IV) species have been  reported. These compounds model biological complexes such as [[cytochrome P450]], [[NO synthase]], and isopenicillin N synthase. Two such reported compounds are thiolate-ligated oxoiron(IV) and cyclam-acetate oxoiron(IV).
Thiolate-ligated oxoiron(IV) is formed by the oxidation of a precursor, [Fe<sup>II</sup>(TMCS)](PF<sub>6</sub>) (TMCS = 1-mercaptoethyl-4,8,11-trimethyl-1,4,8,11-tetraza cyclotetradecane), and 3-5 equivalents of H<sub>2</sub>O<sub>2</sub> at -60 ˚C in [[methanol]]. The iron(IV) compound is deep blue in color and shows intense absorption features at 460&nbsp;nm, 570&nbsp;nm, 850&nbsp;nm, and 1050&nbsp;nm. This species Fe<sup>IV</sup>(=O)(TMCS)+ is stable at -60 ˚C, but decomposition is reported as temperature increases. Compound 2 was identified by [[Mössbauer spectroscopy]], high resolution electrospray ionization mass spectrometry ([[ESI-MS]]), [[x-ray absorption spectroscopy]], x-ray absorption fine structure ([[EXAFS]]), [[UV-visible spectroscopy]] (UV-vis), Fourier transform infrared spectroscopy ([[FT-IR]]), and results were compared to [[density functional theory|DFT-calculations]].<ref>Bukowski, M. R., Koehntop, K. D., Stubna, A., Bominaar E. L., Halfen, J. A., Munck, E., Nam, W., Que, L., Science, 310, 1000-1002, 2005; {{DOI|10.1126/science.111909}}</ref>
[[Image:Fe4TMCOOTf2.png|thumb|120px|right|tetramethylcyclam supported oxoiron(IV)]]
[[Cyclam|Tetramethylcyclam]] oxoiron(IV) is formed by the reaction of Fe<sup>II</sup>(TMC)(OTf)<sub>2</sub>, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; OTf = CF<sub>3</sub>SO<sub>3</sub>, with iodosylbenzene (PhIO) in CH<sub>3</sub>CN at -40 ˚C. A second method for formation of cyclam oxoiron(IV) is reported as the reaction of Fe<sup>II</sup>(TMC)(OTf)<sub>2</sub> with 3 equivalents of H<sub>2</sub>O<sub>2</sub> for 3 hours. This species is pale green in color and has an absorption maximum at 820&nbsp;nm. It is reported to be stable for at least 1 month at -40 ˚C.  It has been characterized by Mössbauer spectroscopy, ESI-MS, EXAFS, UV-vis, [[Raman Spectroscopy]], and FT-IR.<ref>Rohde, J.-U., In, J.-H., Lim, M. H., Brennessel, W. W., Bikowski, M. R., Stubna, A., Munck, E., Name, W., Que, L., Science, 299, 1037-1039, 2003; {{DOI|10.1126/science.299.5609.1037}}</ref>
 
High-valent iron [[bispidine]] complexes are able to oxidize [[cyclohexane]] to [[cyclohexanol]] and [[cyclohexanone]] in 35% yield with an alcohol to ketone ratio up to 4.<ref>Comba, P. et al.; Inorg. Chem., 2009, 48 (21), pp 10389–10396; {{DOI|10.1021/ic901702s}}</ref>
 
===Fe(V)O===
Fe<sup>V</sup>TAML(=O), [[TAML]] = tetraamido macrocyclic ligand, is formed by the reaction of [Fe<sup>III</sup>(TAML)(H<sub>2</sub>O)](PPh<sub>4</sub>) with 2-5 equivalents of meta-chloroperbenzoic acid at -60 ˚C in n-butyronitrile. This compound has a deep green color with absorption maxima at 445 and 630&nbsp;nm.  It is reported to be stable for at least 1 month at 77 K. Fe<sup>V</sup>TAML(=O) was characterized with electron paramagnetic resonance (EPR), Mössbauer, EXAFS, ESI-MS, reactivity studies, and DFT calculations. This compound is capable of 1 electron oxidation at the metal as opposed to at the ligand.  This is due to the stronger –donor capacity of deprotonated amide nitrogens on TAML.<ref>Oliveira, F. T., Chanda, A., Banerjee, D., Shan, X., Mondal, S., Que, L., Bominaar, E. L., Munck, E., Collins, T. J., Science, 315, 835-838, 2007; {{DOI| 10.1126/science.1133417}}</ref>
 
===Electronic structure===
The electronic structure of porphyrin oxoiron compounds has been reviewed.<ref>'''Review''': Fujii, H.; Coordination Chemistry Reviews Volume 226, Issues 1-2, March 2002, Pages 51-60; {{DOI|10.1016/S0010-8545(01)00441-6}}</ref>
 
==Nitridoiron<ref>'''Review''': Berry, J.F.; Comments on Inorganic Chemistry, 30: 28–66, 2009; {{DOI|10.1080/02603590902768875}}</ref> & imidoiron<ref>'''Review''': Peters, J.C., Mehn, M.P.; Journal of Inorganic Biochemistry Volume 100, Issue 4, April 2006, Pages 634-643; {{doi|10.1016/j.jinorgbio.2006.01.023}}</ref> compounds==
[[Image:wieghardt.png|thumb|240px|right|generation of an nitridoiron(VI) complex]]
[[Transition metal nitrido complex|Nitrido-]] and imidoiron-compounds are closely related to [[Haber process|iron-dinitrogen chemistry]].<ref>'''Review:''' Tyler, D. R., Crossland, J. E.; Coordination Chemistry Reviews 254 (2010) 1883–1894; {{DOI|10.1016/j.ccr.2010.01.005}}</ref> The biological significance of nitridoiron(V) porphyrins has been reviewed<ref>'''Review''': Nakamoto, K.; Coordination Chemistry Reviews
Volume 226, Issues 1-2, March 2002, Pages 153-165; {{DOI|10.1016/S0010-8545(01)00425-8}}</ref><sup>,</sup>.<ref>'''Review''': Nakamoto, K.; Journal of Molecular Structure Volumes 408-409, 1 June 1997, Pages 11-16; {{DOI|10.1016/S0022-2860(96)09670-6}}</ref> A widely applicable method to generate high-valent nitridoiron species is the thermal or photochemical oxidative elimination of molecular nitrogen from an azide complex.
:<math>\mathrm{(L)Fe^{n}N_{3} \longrightarrow (L)Fe^{n+2}N + N_{2}}</math>
:<small>symbolic oxidative elimination of nitrogen yields a nitridoiron complex, L denotes the supporting ligand </small>
 
===Fe(IV)N===
Several structurally characterized nitridoiron(IV)-compounds exist <ref>Peters, Jonas C.; Que, Lawrence, Jr. et al.; Inorg. Chem., 2007, 46 (14), pp 5720–5726; {{DOI|10.1021/ic700818q}}</ref><sup>,</sup><ref>Smith et al.; Angewandte Chemie International Edition Volume 48, Issue 17, pages 3158–3160, April 14, 2009; {{DOI|10.1002/anie.200900381}}</ref><sup>,</sup>.<ref>Meyer et al.; Angewandte Chemie International Edition Volume 47, Issue 14, pages 2681–2684, March 25, 2008, April 14, 2009; {{DOI|10.1002/anie.200800600}}</ref>
 
===Fe(V)N===
The first nitridoiron(V)-compound was generated and characterized in 1988/1989 by Wagner and Nakamoto using [[photolysis]] and [[Raman spectroscopy]] at low temperatures <ref>Wagner, W.D.; Nakamoto, K.; J. Am. Chem. Soc., 1989, 111 (5), pp 1590–1598; {{DOI|10.1021/ja00187a010}}</ref><sup>,</sup>.<ref>Wagner, W.D.; Nakamoto, K.; J. Am. Chem. Soc., 1988, 110 (12), pp 4044–4045; {{DOI|10.1021/ja00220a057}}</ref>
 
===Fe(VI)N===
A second Fe<sup>VI</sup> species apart from the [[ferrate]] ion, [(Me<sub>3</sub>cy-ac)FeN](PF<sub>6</sub>)<sub>2</sub>, has been reported. This species, is formed by oxidation followed by [[photolysis]] to yield the Fe(VI) species.  Characterization of the Fe(VI) complex was done by Mossbauer, EXAFS, IR, and DFT calculations.  Unlike the ferrate ion compound 5 is [[diamagnetic]].<ref>Berry, J. F., Bill, E., Bothe, E., George, S. D., Miener, B., Neese, F., Wieghardt, K., Science, 312, 1937-1941, 2006; {{DOI|10.1126/science.1128506}}</ref>
 
===µ-nitrido compounds & oxidation catalysis<ref>Review: Que, L., Tolman, W.B.; Nature 455, 333-340 (18 September 2008); {{DOI|10.1038/nature07371}}</ref>===
Bridged µ-nitrido di-iron [[phthalocyanine]] compounds catalyze the oxidation of [[methane]] to [[methanol]], [[formaldehyde]] and [[formic acid]] using [[hydrogen peroxide]] as sacrificial oxidant.<ref>Sorokin, A.B.; Kudrik, E.V.; Bouchu, D.; Chem. Commun., 2008, 2562-2564; {{DOI|10.1039/B804405H}}</ref>
 
===Electronic structure===
Nitridoiron(IV/V)-species were first explored theoretically in 2002.<ref>Dey, A.; Ghosh, A.; J. Am. Chem. Soc., 2002, 124 (13), pp 3206–3207; {{DOI|10.1021/ja012402s}}</ref>
 
==References==
<references/>
 
==Further reading==
* high-valent manganese: [[Jacobsen's catalyst]]
See also:
Solomon et al.; Angewandte Chemie International Edition Volume 47, Issue 47, pages 9071–9074, November 10, 2008; {{DOI|10.1002/anie.200803740}}
 
{{DEFAULTSORT:High-Valent Iron}}
[[Category:Iron]]

Revision as of 18:37, 23 February 2014

Around for additional than a decade, the tried and correct Victorinox SwissTool can manage just about something. Sporting blunt-nosed pliers, handles that double as a nine-inch ruler and an astounding variety of 24 total folding tools, it's not wonder why the SwissTool is an old favorite.



The Crunch multitool is a little diverse from the rest. It is built about locking pliers (vise-grips) which are significant adequate to grab a 1-inch pipe. The Crunch has been about for over ten years now and still going sturdy due to its distinctive function set. It's roughly about the similar size as the well-known models like the Wave – with a closed length of four inches. I genuinely like the Crunch mostly due to the fact of the locking pliers and its compact size. Seldom do you obtain a toolset like this such as vise-grips in such a tiny package. If you cherished this post and you would like to receive additional facts with regards to top rated pocket Knives kindly take a look at our own page. Top quality engineering and the standard Leatherman fit and feel we've come to expect. 8. Leatherman Super Tool 300 (approx. $65) Cutting end-cutting blades permit multi-tools to make plunge and flush cuts in little locations with no kickback

The demands of an IT tech when it comes to finding the ideal multitool are very various from that of a camper, or hiker. I am nonetheless on the lookout for the most effective multitool as described above but I have yet to find one that incorporates all those functions or essentially any of these characteristics except the pliers of course. An IT tech desires a multitool that has pliers. Pliers with built-in wire strippers to replace the wire cutters generally constructed-in to inside portion of pliers would be great. The wire stripper doesn't have to have to have slots for ten distinctive wire sizes. Two typical gauges would work just fine.

So there you have it, my top rated ten list of the very best multitools offered nowadays. Check out my in-depth comparison table below for all the essential specs at a glance. What ever you decide on, no doubt it will make an excellent addition to your pocket, utility drawer, or tackle box. And recall, multitools make good gifts for Father's Day, Birthdays, Graduation and Groomsmen! What about the other guys? The locking method for each of the person tools is innovative. Each and every tool has it's personal lock that just about appears like piano keys. Having said that, you have to pay consideration and make sure it locks in spot simply because it can be a little challenging getting the lock to engage. For immediate access to all of our deals and discounts, download the DealNews app. Recent Most effective-in-Class Reviews