Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides

Abstract

Three organotin-oxido clusters were formed by hydrolysis of ferrocenyl-functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [R(Fc) SnCl3 ⋅HCl] (C; R(Fc) = CMe2 CH2 C(Me)=N-N=C(Me)Fc) and [SnCl6 ](2-) formed {(R(Fc) SnCl2 )3 [Sn(OH)6 ]}[SnCl3 ] (3 a) and {(R(Fc) SnCl2 )3 [Sn(OH)6 ]}[PhSeO3 ] (3 b), bearing an unprecedented [Sn4 O6 ] unit, in a one-pot synthesis or stepwise through [(R(Fc) SnCl2 )2 Se] (1) plus [(R(Fc) SnCl2 )SePh] (2). A one-pot reaction starting out from FcSnCl3 gave [(FcSn)9 (OH)6 O8 Cl5 ] (4), which represents the largest Fc-decorated Sn/O cluster reported to date.

Acid‐ or Base‐Induced Rearrangements of Ferrocenyl‐Decorated Organotin Sulfide Cages

“…The Sn–S distances involving Sn1 and Sn2 in 2b , without metal–organic decoration but with trigonal bipyramidal coordination by four S atoms and one O atom, vary only a little more, between 2.382(6) and 2.450(6) Å. The Sn–O distances are slightly longer on average (2.158 Å) than those in 2a (2.136 Å on average), but still similar to the values reported for other Fc‐functionalized Sn/O clusters 13. The C–N, N–N, and C–O distances within the conjugated system [–C=N–N=C–O – ] in both compounds, [1.277(8)–1.325(9), 1.379(8)–1.394(7), and 1.297(8)–1.315(7) Å, respectively, for 2a ; 1.19(3)–1.38(3), 1.28(3)–1.444(19), and 1.27(2)–1.35(2) Å, respectively, for 2b ] are between their corresponding single‐ and double‐bond values (C=N/C–N, N=N/N–N, C=O/C–O: 1.29/1.47, 1.25/1.45, and 1.21/1.43 Å, respectively),14 as expected, owing to electron delocalization.…”

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

“…The photophysics of the cluster were recently cemented by Zhu and coworkers [8] with an in-depth structure-property relationship study of it and the related framework [Ag 62 S 12 (S t Bu) 32 ] 2+ , which contains a "metallic" core. These studies complement recent findings showing how silver-thiolate surfaces can stabilize larger Ag cores in atomically precise nanoclusters.[9]In addition to their optical properties, the stabilization of the surfaces in these clusters with thiolate ligands offers an opportunity to incorporate specific chemical properties into the frameworks.[10] With this in mind, the incorporation of multiple ferrocenyl units onto nanoclusters of Ag 2 S was reported in 2010.[11] The targeted synthesis of polyferrocenyl assemblies on inorganic supports is attracting significant research focus because of the electrochemical properties of the frameworks, which offer potential applications as redoxactive and/or luminescent sensors, [12] and as electrode materials.[13] In metal cluster chemistry, supports for such assemblies include the aforementioned metal-chalcogen frameworks, [11, 14] gold nanoparticles, [12a, 15] polyoxometalates [16] and, recently, tin-chalcogenide clusters as developed by Dehnen and co-workers. [17] We had previously prepared the reagent Fc(C{O}OCH 2 CH 2 SSiMe 3 ) (Fc = [CpFe(C 5 H 4 )]), which, when treated with silver acetate and S(SiMe 3 ) 2 , yielded surface functionalized, high-nuclearity Ag 2 S clusters with ferrocene-rich surfaces.…”

“…[11] Thet argeted synthesis of polyferrocenyl assemblies on inorganic supports is attracting significant research focus because of the electrochemical properties of the frameworks,w hich offer potential applications as redoxactive and/or luminescent sensors, [12] and as electrode materials. [13] In metal cluster chemistry,supports for such assemblies include the aforementioned metal-chalcogen frameworks, [11,14] gold nanoparticles, [12a,15] polyoxometalates [16] and,r ecently,t in-chalcogenide clusters as developed by Dehnen and co-workers. [17] We had previously prepared the reagent Fc(C{O}OCH 2 CH 2 SSiMe 3 )( Fc = [CpFe(C 5 H 4 )]), which, when treated with silver acetate and S(SiMe 3 ) 2 ,y ielded surface functionalized, high-nuclearity Ag 2 Sclusters with ferrocene-rich surfaces.…”

Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE3]3− Anions (T=Si, Sn; E=S, Se)

“… [38] The synthetic protocol was expanded for clusters comprising coinage metal atoms to the Ge congeners and to corresponding Ag and Au compounds. [ 34 , 36 , 37 , 38 , 48 , 49 , 50 , 51 , 52 , 53 ] A combined organic‐inorganic extension of the substituents was possible by decoration of clusters with metallocenes,[ 49 , 54 , 55 , 56 , 57 , 58 , 59 ] or with chelate ligands to trap transition metals from solution. [60] To the best of our knowledge, corresponding ternary Si clusters have not yet been reported in the literature.…”