Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations

Abstract

The oxidation of Fe(CO)5 with the [NO]+ salt of the weakly coordinating perfluoroalkoxyaluminate anion [F‐{Al(ORF)3}2]− (RF=C(CF3)3) leads to stable salts of the 18 valence electron (VE) species [Fe(CO)4(NO)]+ and [Fe(CO)(NO)3]+ with the Enemark–Feltham numbers of {FeNO}8 and {FeNO}10. This finally concludes the triad of heteroleptic iron carbonyl/nitrosyl complexes, since the first discovery of the anionic ([Fe(CO)3(NO)]−) and neutral ([Fe(CO)2(NO)2]) species over 80 years ago. Both complexes were fully characterized (IR, Raman, NMR, UV/Vis, scXRD, pXRD) and are stable at room temperature under inert conditions over months and may serve as useful starting materials for further investigations.

Group 6 Hexacarbonyls as Ligands for the Silver Cation: Syntheses, Characterization, and Analysis of the Bonding Compared with the Isoelectronic Group 5 Hexacarbonylates

“…During our continuous efforts to prepare novel transition metal carbonyl [10, 11] and nitrosyl [12, 13] cations as salts of the very good weakly coordinating anions [14] (WCAs) [Al(OR F ) 4 ] −[15] and [F‐{Al(OR F ) 3 } 2 ] − (R F =C(CF 3 ) 3 ), [16] we conducted experiments towards the synthesis of the homoleptic group 6 carbonyl radical cations [Mo(CO) 6 ] + and [W(CO) 6 ] + [17] . An unsuccessful oxidation attempt of W(CO) 6 led to light‐yellow crystals of [Ag{W(CO) 6 } 2 ] + [F‐{Al(OR F ) 3 } 2 ] − .…”

“…During our continuous efforts to preparen ovel transition metal carbonyl [10,11] and nitrosyl [12,13] cations as salts of the very good weakly coordinating anions [14] (WCAs) [Al(OR F ) 4 ] À [15] and [ [F-{Al(OR F )…”

Not Guilty on Every Count: The “Non‐Innocent” Nitrosyl Ligand in the Framework of IUPAC′s Oxidation‐State Formalism

“…Missing a consistent guideline, the nitrosyl metal community has continued to apply workarounds for the assignment of OSs such as taking the nearest integers of net charges obtained from population analyses . In the two‐bond scenario of a metal nitrosyl, however, net charges and the IA‐derived OSs may actually come out with different signs, as will be shown below.…”

Nicht in jedem Punkt schuldig: Der “nicht‐unschuldige” Nitrosyl‐Ligand in IUPACs Oxidationsstufen‐Empfehlung

“…An Nitrosylmetallkomplexen arbeitende Gruppen haben angesichts der inkonsistenten IUPAC‐Darstellung fortgefahren, die OS ohne die neue Empfehlung anzunähern, zum Beispiel als nächstes Ganzzahliges von Nettoladungen aus Populationsanalysen . Allerdings: In einem durch zwei Bindungen beschriebenen Ligand‐Metall‐Fragment können Nettoladungen und IA‐abgeleitete Oxidationsstufen sogar verschiedene Vorzeichen haben.…”