TY - JOUR
T1 - Synthesis and structural characterization of some 1:1 and 1:2 adducts of silver(I) salts with hindered Pmes3, PPhmes2 and PPh2mes bases (Ph = phenyl, mes = 2,4,6-trimethylpheny1))
AU - Effendy, null
AU - Healy, Peter C.
AU - Marchetti, Fabio
AU - Pettinari, Claudio
AU - Pettinari, Riccardo
AU - Tombesi, Alessia
AU - Skelton, Brian W.
AU - White, Allan H.
PY - 2022/5/24
Y1 - 2022/5/24
N2 - A number of 1:2 or 1:1 Ag(I)X:L complexes formed between silver(I) salts, Ag(I)X, and P-donor ligands (L) PPh(3-n)mesn (‘mes’ = 2,4,6-trimethylphenyl) have been synthesized and spectroscopically and structurally characterized. Ag(I)X:Pmes3 (1:2) (solvated) are of the ionic form [Ag(Pmes3)2]+X−, with linear two-coordinate silver atom environments; for X = C1O4−, CF3SO3− (= 'tfs−'); with X = NO3−, the 1:1 complex [(mes3P)Ag(O,O’–NO3)] is obtained but with Ag(I)tfa ('tfa−' = CF3CO2−), [(mes3P)Ag(O,O'-tfa)(NCMe)] has been defined, incorporating MeCN solvent. The 1:2 adducts with PPhmes3/NO3− and PPh2mes3/C1O4−, tfs−, NO3−, tfa−, ac− (=CH3CO2−), SCN− are all of the form [(X-O,O’)AgL2] (unidentate SCN excepted). Ag(I)I:PPhmes2 (1:1) takes the 'cubane' tetramer form, while Ag(I)SCN:PPh2mes (1:1) adopts the (expanded) chair tetramer alternative. A remarkable Ag(I)I:PPh2mes adduct has been isolated, being of 4:3 (x2) Ag(I)I:L stoichiometry, comprising a pair of Ag4I4 cubane units each with three associated phosphine ligands, fused through a central Ag4I4 four-membered ring, the array being centrosymmetric.
AB - A number of 1:2 or 1:1 Ag(I)X:L complexes formed between silver(I) salts, Ag(I)X, and P-donor ligands (L) PPh(3-n)mesn (‘mes’ = 2,4,6-trimethylphenyl) have been synthesized and spectroscopically and structurally characterized. Ag(I)X:Pmes3 (1:2) (solvated) are of the ionic form [Ag(Pmes3)2]+X−, with linear two-coordinate silver atom environments; for X = C1O4−, CF3SO3− (= 'tfs−'); with X = NO3−, the 1:1 complex [(mes3P)Ag(O,O’–NO3)] is obtained but with Ag(I)tfa ('tfa−' = CF3CO2−), [(mes3P)Ag(O,O'-tfa)(NCMe)] has been defined, incorporating MeCN solvent. The 1:2 adducts with PPhmes3/NO3− and PPh2mes3/C1O4−, tfs−, NO3−, tfa−, ac− (=CH3CO2−), SCN− are all of the form [(X-O,O’)AgL2] (unidentate SCN excepted). Ag(I)I:PPhmes2 (1:1) takes the 'cubane' tetramer form, while Ag(I)SCN:PPh2mes (1:1) adopts the (expanded) chair tetramer alternative. A remarkable Ag(I)I:PPh2mes adduct has been isolated, being of 4:3 (x2) Ag(I)I:L stoichiometry, comprising a pair of Ag4I4 cubane units each with three associated phosphine ligands, fused through a central Ag4I4 four-membered ring, the array being centrosymmetric.
KW - Crystal structures
KW - Infrared spectroscopy
KW - NMR spectroscopy
KW - Silver salts
UR - http://www.scopus.com/inward/record.url?scp=85124767566&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2022.120857
DO - 10.1016/j.ica.2022.120857
M3 - Article
AN - SCOPUS:85124767566
SN - 0020-1693
VL - 535
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
M1 - 120857
ER -