“…The silver atoms thus become four-coordinate (AgO 2 S 2 ) in a quasi- tetrahedral geometry with the Ag−S and Ag−O bond lengths in broad ranges from 2.5426 to 2.8769 Å and from 2.248 to 2.326 Å, respectively, and entertain two metallophilic contacts (Figure ). Phosphine sulfide coordination to silver(I) atoms has been observed previously, − but no μ 3 -coordination has been reported. 4 Subunit [(Ph 3 PS) 4 Ag 6 ] (ORTEP, 50% probability ellipsoids, hydrogen atoms omitted) showing the positions of the sulfur atoms above and below the metallacycle.…”
Crystallization of silver trifluoroacetate from chloroform solutions containing triphenylphosphine sulfide affords a trigonal and a monoclinic form of a 6:4 complex {[CF3C(O)OAg]6(Ph3PS)4} of C2 symmetry with different amounts of chloroform in the crystals. With the Ph3PS components as template molecules, the CF3C(O)OAg units are assembled to form a 6-membered metallacycle codetermined by metallophilic bonding and enclosed by a 24-membered ring [AgOCO]6. A complex of the type [LAgOC(O)CF3]2, with L representing the isocyanide ligand pTolSO2CH2NC, has been shown to have a conventional bicyclic structure with three-coordinate silver atoms engaged in transannular metallophilic interactions.
“…The silver atoms thus become four-coordinate (AgO 2 S 2 ) in a quasi- tetrahedral geometry with the Ag−S and Ag−O bond lengths in broad ranges from 2.5426 to 2.8769 Å and from 2.248 to 2.326 Å, respectively, and entertain two metallophilic contacts (Figure ). Phosphine sulfide coordination to silver(I) atoms has been observed previously, − but no μ 3 -coordination has been reported. 4 Subunit [(Ph 3 PS) 4 Ag 6 ] (ORTEP, 50% probability ellipsoids, hydrogen atoms omitted) showing the positions of the sulfur atoms above and below the metallacycle.…”
Crystallization of silver trifluoroacetate from chloroform solutions containing triphenylphosphine sulfide affords a trigonal and a monoclinic form of a 6:4 complex {[CF3C(O)OAg]6(Ph3PS)4} of C2 symmetry with different amounts of chloroform in the crystals. With the Ph3PS components as template molecules, the CF3C(O)OAg units are assembled to form a 6-membered metallacycle codetermined by metallophilic bonding and enclosed by a 24-membered ring [AgOCO]6. A complex of the type [LAgOC(O)CF3]2, with L representing the isocyanide ligand pTolSO2CH2NC, has been shown to have a conventional bicyclic structure with three-coordinate silver atoms engaged in transannular metallophilic interactions.
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