Enantiopure Phospha[1]ferrocenophanes: Textbook Examples of Through-Space Nuclear Spin-Spin Coupling.

Three enantiopure phospha[1]ferrocenophanes (2R ) equipped with either a phenyl, an isopropyl, or a tert-butyl group at the bridging phosphorus atom were synthesized by a salt-metathesis approach in isolated yields between 52 and 63 %. The chirality in these strained sandwich compounds stems from the planar-chiral ferrocene moiety, which is symmetrically equipped with two iPr groups adjacent to phosphorus. Surprisingly, all three phospha[1]ferrocenophanes show an uncommon through-space nuclear 1 H-31 P coupling. As a result of the embedded symmetry, these new compounds are ideal examples to differentiate between through-space and through-bond coupling mechanisms in NMR spectroscopy.

Chiral bora[1]ferrocenophanes: syntheses, mechanistic insights, and ring-opening polymerizations.

A series of new boron-bridged [1]ferrocenophanes ([1]FCPs) was prepared by salt-metathesis reactions between enantiomerically pure dilithioferrocenes and amino(dichloro)boranes (Et2 NBCl2 , iPr2 NBCl2 , or tBu(Me3 Si)NBCl2 ). The dilithioferrocenes were prepared in situ by lithium-bromine exchange from the respective planar-chiral dibromides (Sp ,Sp )-[1-Br-2-(HR2 C)H3 C5 ]2 Fe (R=Me or Et). In most of the cases, mixtures of the targeted [1]FCPs 4 and the unwanted 1,1'-bis(boryl)ferrocenes 5 were formed. The product ratio depends on the bulkiness of the amino group, the speed of addition of the amino(dichloro)borane, the alkyl group on Cp rings, and in particular on the reaction temperature. The formation of strained [1]FCPs is strongly favored by increased reaction temperatures. Secondly, CHEt2 groups at Cp rings favored the formation of the targeted [1]FCPs stronger than CHMe2 groups. These discoveries open up new possibilities to further suppress the formation of unwanted byproducts by a careful choice of the reaction temperature and through tailoring the bulkiness of CHR2 groups on ferrocene. Thermal ring-opening polymerizations of selected boron-bridged [1]FCPs gave metallopolymers with a Mw of 10 kDa (GPC).

Indium-bridged [1]ferrocenophanes.

Indium-bridged [1]ferrocenophanes ([1]FCPs) and [1.1]ferrocenophanes ([1.1]FCPs) were synthesized from dilithioferrocene species and indium dichlorides. The reaction of Li2fc⋅tmeda (fc = (H4C5)2Fe) and (Mamx)InCl2 (Mamx = 6-(Me2NCH2)-2,4-tBu2C6H2) gave a mixture of the [1]FCP (Mamx)Infc (4(1)), the [1.1]FCP [(Mamx)Infc]2 (4(2)), and oligomers [(Mamx)Infc]n (4(n)). In a similar reaction, employing the enantiomerically pure, planar-chiral (Sp,Sp)-1,1'-dibromo-2,2'-diisopropylferrocene (1) as a precursor for the dilithioferrocene derivative Li2fc(iPr2), equipped with two iPr groups in the α position, gave the inda[1]ferrocenophane 5(1) [(Mamx)Infc(iPr2)] selectively. Species 5(1) underwent ring-opening polymerization to give the polymer 5(n). The reaction between Li2fc(iPr2) and Ar'InCl2 (Ar' = 2-(Me2NCH2)C6H4) gave an inseparable mixture of the [1]FCP Ar'Infc(iPr2) (6(1)) and the [1.1]FCP [Ar'Infc(iPr2)]2 (6(2)). Hydrogenolysis reactions (BP86/TZ2P) of the four inda[1]ferrocenophanes revealed that the structurally most distorted species (5(1)) is also the most strained [1]FCP.

A flexible approach to strained sandwich compounds: chiral [1]ferrocenophanes with boron, gallium, silicon, and tin in bridging positions.

The enantiomerically pure dibromoferrocene 3 [(Sp,Sp )-1,1'-dibromo-2,2'-di(isopropyl)ferrocene], equipped with two iPr groups in α positions, was prepared using known "Ugi amine" chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring-opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0°C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt-metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx =Ga[2-(Me2NCH2)C6H4] (4 a), SiMe2 (4 b), SntBu2 (4 c), BNiPr2 (4 d)]. The new [1]FCPs were fully characterized including single-crystal X-ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b-d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b-d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes.