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''Povzeto po '''Ferrocene''' from Wikipedia, the free encyclopedia:'' https://en.wikipedia.org/wiki/Ferrocene
''Povzeto po '''Ferrocene''' from Wikipedia, the free encyclopedia:'' https://en.wikipedia.org/wiki/Ferrocene


'''Ferocen''' je organokovinska spojina s formulo Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>. Struktura molekule je kompleks, ki je sestavljen iz dveh ciklopentadienilnih obročev vezanih na centralni železov atom. Spojina je oranžna trdna snov, ki ima vonj po kafri. Spojina sublimira nad sobno temperaturo in se topi v večini organskih topil. Spojina je znana po njeni izjemni stabilnosti. Ni občutljiva na vodo, zrak, močne baze, in je termično stabilna do 400 °C, brez razpada kompleksa. V oksidativnih pogojih lahko reverzibilno reagira z močnimi kislinami, da tvori ferocenijev kation Fe(C<sub>5</sub>H<sub>5</sub>)<sup>+</sup><sub>2</sub>.<sup>[8]</sup>
'''Ferocen''' je organokovinska spojina s formulo Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>. Struktura molekule je kompleks, ki je sestavljen iz dveh ciklopentadienilnih obročev vezanih na centralni železov atom. Spojina je oranžna trdna snov, ki ima vonj po kafri. Spojina sublimira nad sobno temperaturo in se topi v večini organskih topil. Spojina je znana po njeni izjemni stabilnosti. Ni občutljiva na vodo, zrak, močne baze, in je termično stabilna do 400 °C, brez razpada kompleksa. V oksidativnih pogojih lahko reverzibilno reagira z močnimi kislinami, da tvori ferocenijev kation Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub><sup>+</sup>.<sup>[8]</sup>
Odkritju ferocena pogosto pripisujejo zasluge za hiter razvoj organokovinske kemije.
Odkritju ferocena pogosto pripisujejo zasluge za hiter razvoj organokovinske kemije.


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Analoge ferocena lahko pripravimo z različicami ciklopentadienila. Dva primera sta bisindeniliron in bisfluoreniliron.<sup>[59]</sup>
Analoge ferocena lahko pripravimo z različicami ciklopentadienila. Dva primera sta bisindeniliron in bisfluoreniliron.<sup>[59]</sup>


Ogljikove atome je mogoče nadomestiti s heteroatomi, kot je prikazano s Fe(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)(η<sup>5</sup>-P<sub>5</sub>) in Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(η<sup>5</sup>-C<sub>4</sub>Hsub>4</sub>N) ("azaferocen"). Azaferocen nastane z dekarbonilacijo Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>(η<sup>1</sup>-pirola) v cikloheksanu.<sup>[77]</sup> Pri vrenju pod refluksom v benzenu se nato pretvori v ferocen.<sup>[78]</sup>
Ogljikove atome je mogoče nadomestiti s heteroatomi, kot je prikazano s Fe(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)(η<sup>5</sup>-P<sub>5</sub>) in Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(η<sup>5</sup>-C<sub>4</sub>H<sub>4</sub>N) ("azaferocen"). Azaferocen nastane z dekarbonilacijo Fe(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>(η<sup>1</sup>-pirola) v cikloheksanu.<sup>[77]</sup> Pri vrenju pod refluksom v benzenu se nato pretvori v ferocen.<sup>[78]</sup>


Zaradi enostavne substitucije je bilo pripravljenih veliko derivatov ferocena z neobičajno strukturo. Na primer penta(ferocenil)ciklopentadienilni ligand <sup>[79]</sup> vsebuje ciklopentadienilni anion, derivatiziran s petimi ferocenskimi substituenti.
Zaradi enostavne substitucije je bilo pripravljenih veliko derivatov ferocena z neobičajno strukturo. Na primer penta(ferocenil)ciklopentadienilni ligand <sup>[79]</sup> vsebuje ciklopentadienilni anion, derivatiziran s petimi ferocenskimi substituenti.


V '''heksaferocenilbenzenu''', C<sub>6</sub>(η<sub>5</sub>-C<sub>5</sub>H<sub>4</sub>)Fe(η<sub>5</sub>-C<sub>5</sub>H<sub>5</sub>)]<sub>6</sub>, ima vseh šest položajev na molekuli benzena ferocenilne substituente (R).<sup>[80]</sup> Rentgenska difrakcijska analiza te spojine potrjuje, da ciklopentadienilni ligandi niso koplanarni z benzenskim jedrom, ampak imajo izmenične diedrske kote +30° in −80°. Zaradi sterične oviranosti so ferocenili rahlo upognjeni s koti 177° in imajo podaljšane C-Fe vezi. Kvarterni ciklopentadienilni ogljikovi atomi so prav tako piramidalizirani. Poleg tega ima benzenovo jedro konformacijo stola z diedričnimi koti 14° in prikazuje spreminjanje dolžine vezi med 142,7 pm in 141,1 pm, kar kaže na sterično oviranost substituentov.
V '''heksaferocenilbenzenu''', C<sub>6</sub>(η<sub>5</sub>-C<sub>5</sub>H<sub>4</sub>)Fe(η<sub>5</sub>-C<sub>5</sub>H<sub>5</sub>)<sub>6</sub>, ima vseh šest položajev na molekuli benzena ferocenilne substituente (R).<sup>[80]</sup> Rentgenska difrakcijska analiza te spojine potrjuje, da ciklopentadienilni ligandi niso koplanarni z benzenskim jedrom, ampak imajo izmenične diedrske kote +30° in −80°. Zaradi sterične oviranosti so ferocenili rahlo upognjeni s koti 177° in imajo podaljšane C-Fe vezi. Kvarterni ciklopentadienilni ogljikovi atomi so prav tako piramidalizirani. Poleg tega ima benzenovo jedro konformacijo stola z diedričnimi koti 14° in prikazuje spreminjanje dolžine vezi med 142,7 pm in 141,1 pm, kar kaže na sterično oviranost substituentov.


Objavljena je bila sinteza heksaferocenilbenzena z uporabo Negishijeve sklopitve heksajodidobenzena in diferocenilcinka z uporabo tris(dibenzilidenaceton)dipaladija(0) kot katalizatorja v tetrahidrofuranu: <sup>[80]</sup>  
Objavljena je bila sinteza heksaferocenilbenzena z uporabo Negishijeve sklopitve heksajodidobenzena in diferocenilcinka z uporabo tris(dibenzilidenaceton)dipaladija(0) kot katalizatorja v tetrahidrofuranu: <sup>[80]</sup>  
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== Glej tudi ==
== Glej tudi ==
*Josiphosovi ligandi
*[https://en.wikipedia.org/wiki/Josiphos_ligands Josiphosovi ligandi]


==Sklici==
==Sklici==
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Latest revision as of 15:54, 7 January 2023

Povzeto po Ferrocene from Wikipedia, the free encyclopedia: https://en.wikipedia.org/wiki/Ferrocene

Ferocen je organokovinska spojina s formulo Fe(C5H5)2. Struktura molekule je kompleks, ki je sestavljen iz dveh ciklopentadienilnih obročev vezanih na centralni železov atom. Spojina je oranžna trdna snov, ki ima vonj po kafri. Spojina sublimira nad sobno temperaturo in se topi v večini organskih topil. Spojina je znana po njeni izjemni stabilnosti. Ni občutljiva na vodo, zrak, močne baze, in je termično stabilna do 400 °C, brez razpada kompleksa. V oksidativnih pogojih lahko reverzibilno reagira z močnimi kislinami, da tvori ferocenijev kation Fe(C5H5)2+.[8] Odkritju ferocena pogosto pripisujejo zasluge za hiter razvoj organokovinske kemije.


Zgodovina

Odkritje

Ferocen je bil nepričakovano odkrit trikrat v svoji zgodovini. Prva znana sinteza je morda bila izvedena okoli leta 1940, ko so raziskovalci podjetja “Union Carbide” skušali poslati hlape ciklopentadiena skozi železno cev. Hlapi so reagirali s steno cevi, kar je ustvarilo “rumeno sluz”, ki je cev zamašila. Leta kasneje je shranjen vzorec sluzi pridobil in analiziral E. Brimm, nedolgo zatem, ko je prebral Kealy in Pausonov članek. Odkril je, da je vzorec vseboval ferocen. [8] [9]

Druga sinteza je bila okoli leta 1950, ko so S. Miller, J. Tebboth in J. Tremaine, raziskovalci podjetja “British Oxygen”, skušali sintetizirati amine iz ogljikovodikov in dušika, z uporabo modificiranega Haber procesa. Ko so skušali reagirati ciklopentadien z dušikom pri 300 °C in atmosferskem tlaku, so opazili, da je ogljikovodik reagiral z virom železa, kar je vodilo do tvorbe ferocena. Čeprav so opazili, da ima nastala spojina izjemno dobro stabilnost, so opažanja dali na stran in jih objavili šele zatem, ko je Pauson objavil svoja odkritja. [8] [10] [11] Kealy in Pauson sta celo od Millerja in ostalih raziskovalcev “British Oxygen” pridobila vzorec, s katerim sta potrdila, da gre za isto spojino.

Leta 1951 sta Peter L. Pauson in Thomas J. Kealy, iz Univerze Duquesne v Pittsburgh, Pensilvaniji, poskušala pripraviti fulvalen ((C5H4)2), z oksidativno dimerizacijo ciklopentadiena (C5H6). V procesu sta zreagirala Grginardov reagent ciklopentadienil magnezijev bromid in dietil eter, z železovim kloridom, ki je imel vlogo oksidanta. Namesto pričakovanega fulvalena sta pridobila oranžen prah z “izjemno stabilnostjo”. Formula prahu je bila C10H10Fe. [9] [12]

Določevanje strukture

Pauson in Kealy sta ugibala, da je spojina imela dve ciklopentadienilni skupini, vsaka z eno enojno kovalentno vezjo iz nasičenega ogljikovega atoma na atom železa.[8] Predlagana struktura je bila neskladna z veznimi modeli in ni razložila nepričakovane stabilnosti spojine. Kemiki so imeli težave z ugotavljanjem pravilne strukture.[11] [13] Strukturo so neodvisno določile in objavile tri skupine, leta 1952:[14]

  • Woodward in Wilkins sta jo določila ob opažanju, da je ferocen sodeloval v reakcijah, ki so značilne za aromatske spojine, kot je benzen[15]
  • E. Fischer je določil strukturo(poimenoval jo je “dvojni stožec”) in sintetiziral še druge metalocene, kot sta niklocen in kobaltocen [16] [17] [18]
  • P. F. Eiland in R. Pepinsky sta potrdila strukturo z rentgensko kristalografijo in kasneje z NMR analizo.[11] [19] [20] [21]

Razumevanje strukture

“Sendvič” struktura ferocena je bila osupljivo odkritje in je za njeno razlago potrebovala nove teorije. Uporaba teorije molekulskih orbital, ob predpostavki, da se med dvema ciklopentadienilnima anionoma(C5H5)- nahaja Fe2+ kovinski center, je vodila do uspešnega Dewar-Chatt-Duncanson modela, ki pa je omogočil pravilni napoved geometrije molekule in obrazložil njeno izjemno stabilnost.[22] [23]

Vpliv

Ferocen ni bila prva odkrita organokovinska spojina. Zeisova sol K[PtCl3(C2H4)]·H2O je bila odkrita leta 1831,[24][25] Mond je Ni(CO)4 odkril leta 1888[26] in organolitijeve spojine pa so bile razvite leta 1930.[27] Kljub temu pa je je odkritje ferocena nedvomno vodilo do obravnavanja organokovinske kemije, kot ločeno vejo kemije, hkrati pa je vodilo je tudi do povečanega interesa za spojine kovin d-bloka z ogljikovodiki.

Odkritje strukture je bilo tako pomembno, da sta Wilkinson in Fischer, leta 1973, prejela Nobelovo nagrado za kemijo za njuno delo z organokovinsko kemijo in “sendvič” spojinami.[28]

Zgradba in vezava

Mössbauerjeva spektroskopija kaže na to, da naj bi železov ion v ferocenu imel oksidacijsko stanje +2. Vsak ciklopentadienilski obroč ima tako naboj 1-. Ferocen se zato lahko opiše kot železov (II) bis(ciklopentadienid), Fe2+[C5H-5]2 Na vsakem obroču se nahaja 6 π-elektronov, kar pomeni, da so ti,Hückel-ovem pravilu, aromatski. Teh 12 π-elektronov se prenaša med kovino in obroči prek kovalentne vezi. Ker ima Fe2+ 6 d-elektronov, ima kompleks 18-elektronsko konfiguracijo, kar poveča njegovo stabilnost. V moderni notaciji prikažemo strukturni model ferocena kot Fe(η5-C5H5)2.

Dolžine vseh C-C vezi vsakega petčlenskega obroča znašajo 1.40 Å, dolžine vezi Fe–C pa znašajo 2.04 Å. V območju od sobne temperature do 164K rentgenska kristalografija pokaže monoklinski kristalni sistem; ciklopentadienidni obroči imajo ‘staggered’ konformacijo, kar vodi v centrosimetrično molekulo s točkovno skupino D5d.[19] Pod 110 K ferocen kristalizira kot ortorombska kristalna mreža, v kateri so obroči ciklopentadienila urejeni in zasenčeni tako, da ima molekula točkovno skupino D5h. [29] V plinasti fazi nam elektronska difrakcija[30] in računske metode[31] pokažejo, da so obroči ciklopentadienila zasenčeni.

Ciklopendatienilski obroči se rotirajo okoli Cpcentroid–Fe–Cpcentroid osi, kar nam kažejo meritve na substituiranih derivatih ferocena z uporabo 1H and 13C NMR spektroskopije. Kot primer metilferocen(CH3C5H4FeC5H5) kaže singlet za C5H5 obroč.[32]

Sinteza

Industrijska sinteza

Industrijsko se ferocen sintetizira z reakcijo železovega(II)etoksida s ciklopentadienom;[33] železov(II)etoksid se pridobi z elektrokemijsko oksidacijo kovinskega železa v brezvodnem etanolu. Pri tej reakciji kot stranski produkt nastane etanol, ki sodeluje v sintezi kot katalizator. Celokupna reakcija je: Fe + 2C5H6 → H2 + Fe(C5H6)2.

Preko Grignard-ovega reagenta

Prve sinteze ferocena so bile objavljene istočasno. Pauson in Kealy sta sintetizirala ferocene z uporabo železovega(III)klorida in Grignard-ovega reagena (ciklopentadienil magnezijev bromid). Železov(III)klorid se vnese v brezvodni dietil eter in se ga doda Grignard-ovemu reagent.[12] Poteče redoks reakcija, pri kateri nastane ciklopentadienilski radikal in železovi(II) ioni. Dihidrofulvalen nastane z radikalso rekombinacijo, ko železo(II) reagira z Grignardovim reagentom, da nastane ferocen. Oksidacija dihidrofulvalena v fulvalen z železom(III) ne poteče.[9]

Plin-kovinska reakcija

Drugo sintezo ferocena je izvedel Miller et al[10], ki je kovinsko železo reagiral z ciklopentadienom v plinski fazi pri povišani temperaturi.[34] Objavljen je bil tudi poskus sinteze z uporabo železovega pentakarbonila.

Fe(CO)5 + 2 C5H6(g) → Fe(C5H5)2 + 5 CO(g) + H2(g)

Preko alkalijskega ciklopentadienida

Bolj učinkovita priprava je običajno modifikacija transmetalacijske sekvence z uporabo natrijevega ciklopentadienida[36] oziroma ciklopentadiena, deprotoniranega s kalijevim hidroksidom[37]. Ti reagirajo z brezvodnim železovim(II) kloridom v eterskih topilih. Moderne modifikacije Pauson in Kealy-eve originalne reakcije so:

  • Uporaba natrijevega ciklopentadienida: 2 NaC5H5 + FeCl2 → Fe(C5H5)2 + 2 NaCl
  • Uporaba deprotoniranega ciklopentadiena:

FeCl2·4H2O + 2 C5H6 + 2 KOH → Fe(C5H5)2 + 2 KCl + 6 H2O

  • Uporaba železove(II) soli z Grignardovim reagentom:

2 C5H5MgBr + FeCl2 → Fe(C5H5)2 + 2 MgBrCl Tudi nekatere aminske baze (dietilamin) se lahko uporabi za deprotonacijo, ampak reakcija poteče kasneje kot pri deprotonaciji z močno bazo:[36]

2 C5H6 + 2 (CH3CH2)2NH + FeCl2 → Fe(C5H5)2 + 2 (CH3CH2)2NH2Cl

Direktna transmetalacija se lahko uporabi za sintezo ferocena iz ostalih metalocenov, kot je manganocen:[38]

FeCl2 + Mn(C5H5)2 → MnCl2 + Fe(C5H5)2

Lastnosti

Ferocen je na zraku stabilna oranžna trdna snov z vonjem po kafri. Kot je pričakovano za simetrično, nenaelektreno spojino, je ferocen topen v običajnih organskih topilih, kot je benzen, vendar je netopen v vodi. Odporen je na temperature do 400 °C.[39]

Ferocen zlahka sublimira, predvsempri segrevanju v vakuumu. Njegov parni tlak je približno 1 Pa pri 25 °C, 10 Pa pri 50 °C, 100 Pa pri 80 °C, 1000 Pa pri 116 °C in 10.000 Pa (skoraj 0,1 atm) pri 162 °C.[40] [41]

Reakcije

Z elektrofili

Ferocen je podvržen številnim reakcijam značilnim za aromatske spojine, kar omogoča pripravo substituiranih derivatov. Pogost poskus je Friedel–Craftsova reakcija ferocena z anhidridom ocetne kisline (ali acetil kloridom) v prisotnosti fosforjeve kisline kot katalizatorja. Pod pogoji za Mannichovo reakcijo ferocen daje N,N-dimetilaminometilferocen.

Protonacija ferocena omogoča izolacijo [Cp2FeH]PF6.[39]

Me2NPCl2 in ferocen reagirata v ferocenil diklorofosfin v prisotnosti aluminijevega klorida [43], medtem ko obdelava s fenildiklorofosfinom pod podobnimi pogoji tvori P,P-diferocenil-P-fenil fosfin.[44]

Ferocen reagira s P4S10 in tvori diferocenil-ditiadifosfetan disulfid.[45]

Litinacija

Ferocen reagira z butillitijem, kjer nastane 1,1'-dilitioferocen, ki je vsestranski nukleofil. V kombinaciji z butillitijem in terc-butillitijem tvori monolitioferocen.[46]

Redoks kemija

Ferocen je podvržen enoelektronski oksidaciji pri približno 0,4 V v primerjavi z nasičeno kalomelno elektrodo (SCE) in postane ferocenij. Ta reverzibilna oksidacija je bila uporabljena kot standard v elektrokemiji kot Fc+/Fc = 0,64 V v primerjavi s standardno vodikovo elektrodo.[47] Poročali so tudi druge vrednsoti.[48] Ferocenijev tetrafluoroborat je pogost reagent.[49] Izjemno reverzibilno oksidacijsko-redukcijsko obnašanje se v veliki meri uporablja za nadzor procesov prenosa elektronov v elektrokemijskih[50] [51] in fotokemijskih[52] [53] sistemih.

Substituenti na ciklopentadienilnih ligandih spremenijo redoks potencial na pričakovan način: skupine, ki odvzemajo elektrone, kot je karboksilna kislina, premaknejo potencial v anodno smer (tj. postanejo bolj pozitivne), medtem ko skupine, ki sproščajo elektrone, kot so metilne skupine, premaknejo potencial v katodno smer (tj. postanejo bolj negativne). Tako je dekametilferocen veliko lažje oksidiran kot ferocen in se lahko oksidira do oksidacijskega števila 2+.[54] Ferocen se pogosto uporablja kot interni standard za kalibracijo redoks potencialov v nevodni elektrokemiji.

Stereokemija substituiranih ferocenov

Disubstituirani feroceni lahko obstajajo bodisi kot 1,2-, 1,3- ali 1,1′- izomeri, ki jih ne moremo pretvarjati med seboj. Feroceni, ki so asimetrično disubstituirani na enem obroču, so kiralni – na primer [CpFe(EtC5H3Me)]. Ta planarna kiralnost nastane kljub temu, da noben atom nima stereocentra. Substituiran ferocen, prikazan na sliki (derivat 4-(dimetilamino)piridina), se je izkazal za učinkovitega pri uporabi kinetičnega ločevanja racemnih sekundarnih alkoholov. [55] Za asimetrično 1,1'-funkcionalizacijo ferocena je bilo razvitih več pristopov. [56]

Uporaba ferocena in njegovih derivatov

Ferocen in njegovi številni derivati ​​nimajo obsežnih aplikacij, imajo pa veliko novih uporab, ki izkoriščajo nenavadno strukturo (ogrodja ligandov, kandidati za farmacevtske izdelke), robustnost (formulacije proti detonaciji, prekurzorji materialov) in redoks lastnosti (reagenti in redoks standardi) ferocena.

Ogrodja ligandov

Kiralni ferocenil fosfini se uporabljajo kot ligandi za reakcije, ki jih katalizirajo kovine prehoda. Nekateri od njih imajo industrijsko uporabo pri sintezi farmacevtskih izdelkov in agrokemikalij. Na primer difosfin 1,1'-bis(difenilfosfino)ferocen (dppf) je cenjen ligand za reakcije spajanja s paladijem, Josiphosov ligand pa je uporaben pri katalitskem hidrogeniranju.[57] Josiphosovi ligandi se imenujejo po tehniku Josiju Puleu, ki je izdelal prvi tak ligand.[58][59]

Dodatki h gorivu

Ferocen in njegovi derivati ​​so sredstva proti detonaciji, ki se uporabljajo v gorivu za bencinske motorje. So varnejši od tetraetilsvinca, ki se je uporabljal pred tem.[60] Raztopine aditivov za bencin, ki vsebujejo ferocen, se lahko dodajo neosvinčenemu bencinu, da se omogoči njegova uporaba v starodobnih avtomobilih zasnovanih za pogon z osvinčenim bencinom.[61] Železne obloge, ki nastanejo iz ferocena, lahko tvorijo prevodno prevleko na površinah vžigalnih svečk. Kopolimeri ferocenskega poliglikola, pripravljeni s polikondenzacijsko reakcijo med derivatom ferocena in substituiranim dihidroksi alkoholom, so obetavni kot sestavina raketnih pogonskih goriv. Ti kopolimeri zagotavljajo raketnim pogonom toplotno stabilnost, služijo kot vezivo pogonskega goriva in nadzorujejo hitrost izgorevanja pogonskega goriva. [62]

Ugotovljeno je bilo, da je ferocen učinkovit pri zmanjševanju dima in žveplovega trioksida, ki nastajata pri sežiganju premoga. Dodajanje majhne količine te kovinske ciklopentadienilne spojine na kateri koli praktični način (impregniranje premoga ali dodajanje ferocena v zgorevalno komoro) lahko znatno zmanjša količino prej omenjenih nezaželenih stranskih produktov.[63]

Farmacevtski izdelki

Derivate ​​ferocena so preučevali kot potencialna zdravila [64], pri čemer je bila spojina feroceron odobrena za uporabo v ZSSR v sedemdesetih letih prejšnjega stoletja, danes pa je ne tržijo več [65]. Samo eno zdravilo je v zadnjih letih vstopilo v klinične študije, ferroquin (7-kloro-N-(2-((dimetilamino)metil)ferocenil)kinolin-4-amin), antimalarik, [66][67][68] ki je dosegel fazo preskušanj IIb.[69] Raziskovali so sisteme za dostavo zdravil na osnovi polimerov, ki vsebujejo ferocen.[70]

Protirakavo delovanje derivatov ferocena je bilo prvič preučevano v poznih sedemdesetih letih dvajsetega stoletja, ko so derivate, ki vsebujejo aminske ali amidne skupine, testirali za zdravljenje limfocitne levkemije.[71] Nekatere ferocenijeve soli kažejo protirakavo delovanje, vendar nobena izmed spojin ni dosegla kliničnih preizkušanj.[72] Derivati ​​ferocena močno zavirajo razvoj pljučnega raka (zavirajo celično linijo A549), raka debelega črevesa in danke (zavirajo celično linijo HCT116) ter raka dojke (zavirajo celično linijo MCF-7).[73] Poročali so o eksperimentalnem zdravilu, ki je ferocenilna različica tamoksifena.[74] Ideja je, da se bo tamoksifen vezal na vezavna mesta estrogena, kar bo povzročilo citotoksičnost.[74][75]

Za namene uporabe proti raku, ferocifene izkorišča francosko biotehnološko podjetje Feroscan, ki ga je ustanovil Pr. Gerard Jaouen.

Trdno raketno gorivo

Ferocen in sorodni derivati ​​se uporabljajo kot močni katalizatorji hitrosti zgorevanja v kompozitnem pogonskem gorivu iz amonijevega perklorata.[76]

Derivati in različice

Analoge ferocena lahko pripravimo z različicami ciklopentadienila. Dva primera sta bisindeniliron in bisfluoreniliron.[59]

Ogljikove atome je mogoče nadomestiti s heteroatomi, kot je prikazano s Fe(η5-C5Me5)(η5-P5) in Fe(η5-C5H5)(η5-C4H4N) ("azaferocen"). Azaferocen nastane z dekarbonilacijo Fe(η5-C5H5)(CO)21-pirola) v cikloheksanu.[77] Pri vrenju pod refluksom v benzenu se nato pretvori v ferocen.[78]

Zaradi enostavne substitucije je bilo pripravljenih veliko derivatov ferocena z neobičajno strukturo. Na primer penta(ferocenil)ciklopentadienilni ligand [79] vsebuje ciklopentadienilni anion, derivatiziran s petimi ferocenskimi substituenti.

V heksaferocenilbenzenu, C65-C5H4)Fe(η5-C5H5)6, ima vseh šest položajev na molekuli benzena ferocenilne substituente (R).[80] Rentgenska difrakcijska analiza te spojine potrjuje, da ciklopentadienilni ligandi niso koplanarni z benzenskim jedrom, ampak imajo izmenične diedrske kote +30° in −80°. Zaradi sterične oviranosti so ferocenili rahlo upognjeni s koti 177° in imajo podaljšane C-Fe vezi. Kvarterni ciklopentadienilni ogljikovi atomi so prav tako piramidalizirani. Poleg tega ima benzenovo jedro konformacijo stola z diedričnimi koti 14° in prikazuje spreminjanje dolžine vezi med 142,7 pm in 141,1 pm, kar kaže na sterično oviranost substituentov.

Objavljena je bila sinteza heksaferocenilbenzena z uporabo Negishijeve sklopitve heksajodidobenzena in diferocenilcinka z uporabo tris(dibenzilidenaceton)dipaladija(0) kot katalizatorja v tetrahidrofuranu: [80]

Izkoristek je le 4 %, kar je nadaljnji dokaz, da so okoli arenskega centra prisotne velike sterične napetosti.

Kemija materialov

Verige nenabitega polimera, ki je prekurzor nanodelcev železa, se lahko uporablja kot katalizator za proizvodnjo ogljikovih nanocevk.[82] Vinilferocen je mogoče izdelati z Wittigovo reakcijo aldehida, fosfonijeve soli in natrijevega hidroksida.[83] Vinil ferocen je mogoče pretvoriti v polimer (polivinilferocen, PVFc), ki je ferocenilna različica polistirena (fenilne skupine so nadomeščene s ferocenilnimi skupinami). Lahko se tvori tudi drug poliferocen, poli(2-(metakriloiloksi)etil ferocenkarboksilat), PFcMA. Poleg uporabe organskih polimernih ogrodij so lahko viseče ferocenske enote pritrjene na anorganska ogrodja, kot so polisiloksani, polifosfazeni in polifosfinoborani, (–PH(R)–BH2–)n, nastali materiali pa imajo nenavadne fizikalne in elektronske lastnosti, povezane z redoks parom ferocen/ferocinij.[81] Tako PVFc kot PFcMA so nanesli na kremenčev substrat in jima izmerili omočljivost, ko so polimerne verige nenabite in ko so ferocenski deli oksidirani, da nastanejo pozitivno nabite skupine. Kontaktni kot z vodo na substratu, prevlečenim s PFcMA, je bil po oksidaciji manjši za 70°, medtem ko je bilo pri PVFc zmanjšanje za 30° in preklapljanje omočljivosti je reverzibilno. V primeru PFcMA je učinek podaljšanja verig, ter s tem uvedbe več ferocenskih skupin, znatno večje zmanjšanje kontaktnega kota pri oksidaciji.[81] [84]

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