Ag[Fe(CO)₅]₂⁺: A Bare Silver Complex with Fe(CO)₅ as a Ligand

Abstract

Attempts to prepare Fe(CO)5 (+) from Ag[Al(OR(F) )4 ] (R(F) =C(CF3 )3 ) and Fe(CO)5 in CH2 Cl2 yielded the first complex of a neutral metal carbonyl bound to a simple metal cation. The Ag[Fe(CO)5 ]2 (+) cation consists of two Fe(CO)5 molecules coordinating Ag(+) in an almost linear fashion. The ν(CO) modes are blue-shifted compared to Fe(CO)5 , with one band above 2143 cm(-1) indicating that back-bonding is heavily decreased in the Ag[Fe(CO)5 ]2 (+) cation.

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl, Br, I) System

“…Owing to the poor binding energy of the dihalogen bases and the expected high reactivity, we used [Al(OR F ) 4 ] − (R F =C(CF 3 ) 3 ; A − ) as counterion . It stabilizes weakly bound complexes like [Ag(P 4 ) 2 ] + , [Ag(C 2 H 2 ) 4 ] +[10] or [Ag(Fe(CO) 5 ) 2 ] + , and is also compatible with strong electrophiles and oxidants like [CCl 3 ] + , [P 9 ] + , or [NO 2 ] + . Using our new, facile route to donor‐free Ag A ( 1 ), we now prepared ( A )Ag‐I 2 ‐Ag( A ) ( 2 ), [Ag 2 (I 2 ) 4 ] 2+ ( A − ) 2 ( 3 ) and [Ag 2 (I 2 ) 6 ] 2+ ( A − ) 2 ⋅(I 2 ) x ≈0.65 ( 4 ), and investigated the capacity of molecular ( A )Ag‐I 2 ‐Ag( A ) ( 2 ) to serve as an oxidant.…”

Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters

“…However,t here are af ew examples that contain neutralc arbonylc omplexes as donorl igandst om ain-group [12,18] or transition metals, [19][20][21] such as [(OC) 5 Fe!GaCl 3 ] [22] as well as [Ag{Fe(CO) 5 } 2 ] + . [19,23] Overall,t he heterometallic transition-metal carbonyl complexes are dominated by anionic clusters, with just af ew neutral exampless uch as [Ag 4 {Co(CO) 4 } 4 ]. [24] To the best of our knowledge, [Ag{Fe(CO) 5 } 2 ] + [19,23] is the only,a lbeit rather small, cationic ands tructurally characterized heterobimetallic homoleptic transition-metal carbonyl clustersof ar.…”

“…[19,23] Overall,t he heterometallic transition-metal carbonyl complexes are dominated by anionic clusters, with just af ew neutral exampless uch as [Ag 4 {Co(CO) 4 } 4 ]. [24] To the best of our knowledge, [Ag{Fe(CO) 5 } 2 ] + [19,23] is the only,a lbeit rather small, cationic ands tructurally characterized heterobimetallic homoleptic transition-metal carbonyl clustersof ar.…”

Silver Complexes of Dihalogen Molecules

“…Owing to the poor binding energy of the dihalogen bases in the targeted complexes and their expected high reactivity, we decided to use the perfluorinated alkoxyaluminate [Al(OC(CF 3 ) 3 ) 4 ] − ( A − )—one of the best weakly coordinating anions (WCAs)—as counterion . It stabilizes weakly bound complexes like [Ag(P 4 ) 2 ] + , [Ag(C 2 H 2 ) 4 ] +[17] or [Ag(Fe(CO) 5 ) 2 ] + . But in addition, A − is also compatible with strong electrophiles and oxidants like [CCl 3 ] + , [P 9 ] + , or [NO 2 ] + .…”