[{Fe(C5H4)2}3{Ga(C5H5N)}2]: A Trinuclear Gallium-Bridged Ferrocenophane with a Carousel Structure

Abstract

A molecular carousel, that is the appearance of the structure of the title compound [1⋅2 py] (see picture), the first complex of a new structure type prepared by a highly selective condensation reaction from the equally new complex [Fe(C5H4GaMe2)2]. The first gallium bridged [m.m]ferrocenophane [{Fe(C5H4)2}2{GaMe(C5H5N)} 2] is formed as an intermediate; this compound can also be prepared in a planned synthesis and can be converted into [1⋅2 py] by warming. The complex [1⋅2 py] as well as [1⋅2 Et2O] and [1⋅2 DMSO], which were formed by donor exchange, offers various interesting properties, for example, [1⋅2 DMSO] can be reversibly oxidized to the mono‐, di‐, and trication.

Trimagnesium-bridged trinuclear ferrocenophanes cocomplexed with solvated mononuclear alkali metal amide molecules

“…Its connectivity pattern follows that of 2, though the C 2 symmetry about the Mg( 2 No precedent exists for this extraordinary class of heterotrimetallic complex, either in terms of composition or structure. The closest analogy, also reported in 2001, 3 is the homo-main group-metallic gallium-bridged species [{Fe(C 5 H 4 ) 2 } 3 {Ga• (pyridine)} 2 ]. Made by a condensation reaction from a methylgallium precursor as opposed to the novel synergic metallation approach used here, it possesses a similar chiral 'carousel' arrangement of ferrocenyl units linked by two endpositioned Ga atoms [à la Mg(1) and Mg(3) in 4], but is 'missing' a centric metal atom and metal amide component.…”

Gallium and Indium Alkoxides with Hydride, Cyclopentadienediide and Copper(I) tert‐Butoxide as further Components

“…By qualitative analysis we could find no titanium in the compound, suggesting that a transfer of the cyclopentadienyl group from titanium to the indium atom had taken place together with a formal proton abstraction from C 5 H 5 – (considering the integrals in the 1 H NMR spectrum). Transformations of C 5 H 5 (E) (E = mono‐valent metal centered substituent) into C 5 H 4 (E) 2 , C 5 H 4 (E)(E′) or C 5 H 4 (E′)(E′) (E′ = main group metal centered substituent) have been investigated in view of the synthesis of ansa –metallocenes and can be performed with lithium organyls or even metal‐alkoxides followed by salt eliminations:, an instructive example is the formation of C 5 H 4 (SiMe 2 ‐SiMe 2 ) 2 C 5 H 4 , which has some resemblance to 2 (see below) . Interestingly the bridging C 5 H 4 groups in this exemplary compound may connect in 1,1‐, 1,2‐ and 1,3‐positions of the ring due to 1,5‐sigmatropic shifts of the silyl groups, whereas only the 1,1‐bridge is active in 2 .…”

Regioselective Tetrametalation of Ferrocene in a Single Reaction: Extension of s-Block Inverse Crown Chemistry to the d-Block

“…Looking to the future, the propensity of s‐block metals to undergo exchange in reactions with electrophiles makes 1 , in effect, an invaluable synthon10 for a 1,1′,3,3′‐tetraanion of unsubstituted ferrocene. Thus in theory it offers chemists scope for designing new regioselectively tetrasubstituted ferrocenes.…”