A Functionalized Ag₂S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag₇₄S₁₉(dppp)₆(fc(C{O}OCH₂CH₂S)₂)₁₈]

Abstract

A ferrocene-based dithiol 1,1'-[fc(C{O}OCH2CH2SH)2] has been prepared and treated with a Ag(I) salt to form the stable dithiolate compound [fc(C{O}OCH2CH2SAg)2]n (fc=[Fe(η(5)-C5H4)2]). This is used as a reagent for the preparation of the nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] which was obtained in good yield (dppp=1,3-bis(diphenylphosphino)propane).

Ferrocenecarboxylic anhydride: a redetermination

“…Similar torsional geometry is observed in the ruthenium analogue IVOYOY (62.31 ;Micallef et al, 2011), the 1 0 ,2 0 -bissubstituted ferrocene system KAJBUU (57.04 ;Siebler et al, 2010) and the vanadium compound NEWFIE (66.68 ;Elschenbroich et al, 1997). In the bis-ferrocenophanone structure HOVYEY (Liu et al, 2015) where two ferrocene groups are constrained by two anhydride linkages, the two carbonyl groups are still inclined at an O-CÁ Á ÁC-O torsion angle of 27.47 despite the fact that the bridged Cp rings are almost coplanar, suggesting the O-CÁ Á ÁC-O torsion is a mechanism to relieve steric strain in the molecule. (2) 159Symmetry codes: (i) Àx þ 1; Ày; Àz þ 1; (ii) x þ 1 2 ; Ày þ 1 2 ; Àz þ 1; (iii) Àx þ 1 2 ; y þ 1 2 ; z.…”

Structurally Precise Silver Sulfide Nanoclusters Protected by Rhodium(III) Octahedra with Aminothiolates

“…[6,10] As imilar reaction using ad ithiolate metalloligand of fc(COOCH 2 CH 2 S À ) 2 instead of BuS À has also been carried out by Corrigan and co-workers,w hich led to the formation of [Ag 74 S 19 (dppp) 6 {fc(COOCH 2 CH 2 S) 2 } 18 ] with multistep redox properties. [11] Another synthetic method for silver sulfide nanoclusters was shown by Wang and coworkers,w ho prepared [Ag 62 S 13 (S t Bu) 32 ] 4+ by the reaction of AgBF 4 with AgS t Bu;inthis case,the latter acts not only as an S 2À source but also as aprotecting ligand of the cluster. [12] To date,a pproximately 20 structurally precise silver sulfide nanoclusters,t he structures of which were determined by single-crystal X-ray crystallography,h ave been successfully synthesized by employing appropriate Ag + and S 2À sources as well as thiolate and/or phosphine protecting ligands.…”

Structurally Precise Silver Sulfide Nanoclusters Protected by Rhodium(III) Octahedra with Aminothiolates

“…[12] To date,a pproximately 20 structurally precise silver sulfide nanoclusters,t he structures of which were determined by single-crystal X-ray crystallography,h ave been successfully synthesized by employing appropriate Ag + and S 2À sources as well as thiolate and/or phosphine protecting ligands. [6,[8][9][10][11][12][13][14][15] In these cases,o rganic solvents have been used because of the hydrophobic nature of the thiolate and/or phosphine ligands, thereby affording cluster species that are insoluble in water. In addition, most of the structurally precise silver sulfide clusters so far reported are optically inactive,although several optically active clusters have been prepared by using optically pure protecting ligands.…”

“…[6,10] As imilar reaction using ad ithiolate metalloligand of fc(COOCH 2 CH 2 S À ) 2 instead of BuS À has also been carried out by Corrigan and co-workers,w hich led to the formation of [Ag 74 S 19 (dppp) 6 {fc(COOCH 2 CH 2 S) 2 } 18 ] with multistep redox properties. [11] Another synthetic method for silver sulfide nanoclusters was shown by Wang and coworkers,w ho prepared [Ag 62 S 13 (S t Bu) 32 ] 4+ by the reaction of AgBF 4 with AgS t Bu;inthis case,the latter acts not only as an S 2À source but also as aprotecting ligand of the cluster. [12] To date,a pproximately 20 structurally precise silver sulfide nanoclusters,t he structures of which were determined by single-crystal X-ray crystallography,h ave been successfully synthesized by employing appropriate Ag + and S 2À sources as well as thiolate and/or phosphine protecting ligands.…”

“…Another synthetic method for silver sulfide nanoclusters was shown by Wang and co‐workers, who prepared [Ag 62 S 13 (S t Bu) 32 ] 4+ by the reaction of AgBF 4 with AgS t Bu; in this case, the latter acts not only as an S 2− source but also as a protecting ligand of the cluster . To date, approximately 20 structurally precise silver sulfide nanoclusters, the structures of which were determined by single‐crystal X‐ray crystallography, have been successfully synthesized by employing appropriate Ag + and S 2− sources as well as thiolate and/or phosphine protecting ligands . In these cases, organic solvents have been used because of the hydrophobic nature of the thiolate and/or phosphine ligands, thereby affording cluster species that are insoluble in water.…”