Silver Complexes of Dihalogen Molecules

Abstract

The perfluorohexane-soluble and donor-free silver compound Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) prepared using a facile novel route has unprecedented capabilities to form unusual and weakly bound complexes. Here, we report on the three dihalogen-silver complexes Ag(Cl2 )A, Ag(Br2 )A, and Ag(I2 )A derived from the soluble silver compound Ag(A) (characterized by single-crystal/powder XRD, Raman spectra, and quantum-mechanical calculations).

Homoleptic Trichloroacetonitrile Complexes

“…The silver salt of [Al(O R F ) 4 ] – already proved its ability to coordinate and stabilize weak ligands like C 2 H 4 , C 2 H 2 , P 4 , or S 8 , and recently also the synthesis of complexes with the very weakly coordinating halogene X 2 ( X = Cl, Br, I) as ligands were obtained , . Therefore, the silver salt should be a good starting material for the synthesis of the first charged metal Cl 3 CCN complexes.…”

“…The silver salt of [Al(OR F ) 4 ]already proved its ability to coordinate and stabilize weak ligands like C 2 H 4 , [8] C 2 H 2 , [9] P 4 , [10] or S 8 , [11] and recently also the synthesis of complexes with the very weakly coordinating halogene X 2 (X = Cl, Br, I) as ligands were obtained. [12,13] Therefore, the silver salt should [6] energies optimized at BP86/def2-TZVP level and with ε r = 8.93 (CH 2 Cl 2 ) and 37.5 (MeCN). b) The formation of the Cl 3 CCN complex was also calculated with ε r = 8.93 because (1) the experimental dielectric constant of Cl 3 CCN is 7.0 [7] and similar to CH 2 Cl 2 , but (2) more importantly the use of the very expensive Cl 3 CCN as a pure solvent is not sensible for cost reasons.…”

“…The lithium cation has two relatively short (in the shown cation 270.09 and 271.1 pm) and two long contacts (302.6 and 302.5 pm) to the anion ( Figure 2). These Li···F contacts are rather long by comparison to those in [Li-Ar F ] 2 [Ar F = 2,4,6-(CF 3 ) 3 C 6 H 2 ] at 223 / 224 pm, [17] or even those in the tight ion pair LiAl(OR F ) 4 (215-221 pm) [13] or most drastic in a bicyclic lithium fluorosilylamide at 185 pm that even shows 1 J Li,F coupling in the NMR spectroscopy. [18] The Li-N bond lengths lie between 208.…”

Facile and systematic access to the least-coordinating WCA [(RFO)3Al–F–Al(ORF)3]− and its more Lewis-basic brother [F–Al(ORF)3]− (RF = C(CF3)3)

“…With this anion shown in Scheme 1 , a large variety of reactive cations being electrophilic like [CX 3 ] + , RZn + (R = Me, Et), [Sn(Cp)] + , [P 2 X 5 ] + (X = Cl, Br, I) and [P 9 ] + , oxidizing like [NO] + , [NO 2 ] + or [Ag(X 2 ) n ] + -complexes, or very weakly bound to a central atom like the huge number of [M(L) n ] + complexes with M = Cu, Ag, Au and L = CO, C 2 H 2 , C 2 H 4 , P 4 , S 8 , S 12 , Se 6 , Se 12 or Se 19 could be stabilized. 1 – 5 One of the biggest advantages of this [Al(OR F ) 4 ] – anion is its facile and fast synthesis in high yields. 6 Other commonly used WCAs are [B(C 6 F 5 ) 4 ] – , perhalogenated carborane anions [R–CB 11 X 12 ] – (X = F, Cl, Br) and the teflates [E(OTeF 5 ) x ] – (E = B, Al, Sb, As, Bi, Nb; x = 4, 6).…”

Anorganische Chemie 2016: Koordinationschemie und Bioanorganik

“…8) Um die Wechselwirkungen zwischen Aluminium-Hydroxo-Spezies zu kontrollieren, haben Limberg und Mitarbeiter ein tripodales Silanol als Hilfsligand entwickelt. 9) Damit lässt sich Al iBu 2 H unter kontrollierten Bedingungen stöchiometrisch hydrolysieren, und die Hydroxidcluster [Al 3 (μ-OH) 3 ] 6+ und [Al 8 (μ 3 -OH) 2 -(μ-OH) 10 X Geklickt hat es beim letzten Vertreter der arsenhaltigen Fünfring-Heterocyclen: Die quantitative Huisgenartige [3+2]-Cycloaddition eines Arsaalkins mit 2-(Azidomethyl)pyridin bildet stereoselektiv ein ebenes 2,3,4-Triazaarsol, das als Chelatligand an ein [Re(CO) 3 Br]-Fragment koordiniert. 21) Wenger und Mitarbeiter berichteten über ein -im bestem Sinn des Wortes -Highlight der Koordinationsverbindungen des Molybdäns: 22 Langsame magnetische Relaxation detektierten Powell, Tang und weitere in makroskopischen, hexagonalen Röhren von 3d-4f-Metallocyclen.…”