Initial Report on Molecular and Electronic Structure of Spherical Multiferrocenyl/tin(IV) (Hydr)oxide [(FcSn)₁₂O₁₄(OH)₆]X₂ Clusters

Abstract

Two spherical organic−inorganic ferrocene-tin (hydr)oxide clusters of general formula [(FcSn) 12 O 14 (OH) 6 ]X 2 (Fc = ferrocenyl, X = nitroso-dicyanmethanide, DCO − and benzoylcyanoxime, PCO − anions) were prepared by the direct hydrolysis of Fc 2 SnCl 2 or FcSnCl 3 precursors in the presence of light-and thermally stable Ag(DCO) or Ag(PCO) salts. Molecular structures of FcSnCl 3 Py 2 (1), Fc 2 SnCl 2 Py 2 (2), [(FcSn) 12 O 14 (OH) 6 ](DCO) 2 (3), and [(FcSn) 12 O 14 (OH) 6 ](PCO) 2 (4) were investigated by X-ray crystallography. Density function theory (DFT) and time-dependent density functional theory (TDDFT) calculations were conducted on FcSnCl 3 Py 2 , Fc 2 SnCl 2 Py 2 , and [(FcSn) 12 O 14 (OH) 6 ] 2+ compounds in order to elaborate electronic structures and assign transitions in UV−vis spectra of these systems. The DFT and TDDFT calculations suggest that the organometallic substituents in the [(FcSn) 12 O 14 (OH) 6 ] 2+ core are rather isolated from each other.

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…In conclusion we have shown that simple tripod‐type diorganotin halides such as MeSi(CH 2 SnRI 2 ) 3 (R=Ph, Me 3 SiCH 2 ) serve as precursors for the synthesis of novel belt‐shaped molecular diorganotin oxides [MeSi(CH 2 SnRO) 3 ] n of unprecedented oktokaideka ( n =18) and trikonta ( n =30) nuclearity. The results obtained fit well into the ongoing interest in large‐sized metaloxido clusters in general [2k] and tinoxido clusters of high nuclearity in particular [5g, 6b, 12, 31, 32] . The concept shown herein holds great potential for future work and we encourage interested readers to step into the field.…”

Structures of Large Tin(IV) Oxo Clusters

“…The most symmetrical Sn 12 O x structure is that of the cationic cluster [R 12 Sn 12 O 14 (OH) 6 ] 2 + (R=iPr, [37] Bu, [19,38] CH 2 Ph, [39] CH 2 SiMe 3 , [40] ferrocenyl). [41] The Sn atoms form a distorted icosahedron, whereof 14 of the 20 triangular faces are capped by μ 3 -O. An alternative description is that the structure consists of a central layer of six edge-sharing [RSnO 4 ] square pyramids and a top and bottom layer of three edge-sharing [RSnO 5 ] octahedra.…”

“…The most symmetrical Sn 12 O x structure is that of the cationic cluster [R 12 Sn 12 O 14 (OH) 6 ] 2+ (R= i Pr, [37] Bu, [19,38] CH 2 Ph, [39] CH 2 SiMe 3 , [40] ferrocenyl) [41] . The Sn atoms form a distorted icosahedron, whereof 14 of the 20 triangular faces are capped by μ 3 ‐O.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Bausteine für dreieckförmige Diorganozinnoxidmakrocyclen

“…Zusammenfassend haben wir gezeigt, dass einfache Dreifuß‐Typ Diorganozinnhalogenide wie MeSi(CH 2 SnRI 2 ) 3 (R=Ph, Me 3 SiCH 2 ) als Edukte für die Synthese neuartiger gürtelförmiger molekularer Diorganozinnoxide [MeSi(CH 2 SnRO) 3 ] n von bisher beispielloser oktokaideka ( n =18) und trikonta ( n =30) Nuklearität dienen. Die erhaltenen Resultate liegen im andauernden Interesse an großformatigen Metalloxoclustern im Allgemeinen [2k] und Zinnoxoclustern hoher Nuklearität im Speziellen [5g, 6b, 12, 31, 32] . Das hier vorgestellte Konzept besitzt großes Potenzial für zukünftige Arbeiten und wir ermutigen interessierte Leser es aufzugreifen.…”