Indium‐Bridged [1]Ferrocenophanes

Bagh, Bidraha; Sadeh, Saeid; Green, Jennifer C.; Müller, Jens

doi:10.1002/chem.201303925

Cited by 25 publications

(15 citation statements)

References 108 publications

(98 reference statements)

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“…Recently, we tackled both problems simultaneously through the introduction of isopropyl groups adjacent to the bridging element, which provide steric protection and act as solubilizing groups (B; Figure 1). [11,12] A particularly interesting family of strained sandwich compounds is that of boron-bridged [1]FCPs: they are the only known [1]FCPs bridged by a 2nd period element.…”

Section: Introductionmentioning

confidence: 99%

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Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

Sadeh

Bhattacharjee

Sarbisheh

et al. 2014

Chemistry A European J

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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).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

Sadeh

Bhattacharjee

Sarbisheh

et al. 2014

Chemistry A European J

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“…The new 1-amino-1′-bromoferrocenes 6a , b can be converted into their lithiated derivatives using 2.1 equiv of n BuLi in a 9/1 solvent mixture of hexanes and thf (Scheme ). We used this uncommon solvent mixture as it worked well for the preparation of chiral [1]FCPs before, when we prepared dilithioferrocene derivatives by lithium–bromine exchange reactions. ,,, Even though this mixture mainly consists of hexanes, the formed dilithio species were soluble. Investigations of the lithiation of 1-bromo-1′-(trimethylsilylamino)ferrocene ( 1 ; Scheme ) had shown that a stepwise process was needed to cleanly produce the targeted dilithio compound.…”

Section: Resultsmentioning

confidence: 99%

[n]Ferrocenophanes (n = 2, 3) with Nitrogen and Phosphorus in Bridging Positions

2016

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The in situ prepared dilithio derivative of the known species 1-bromo-1'-(trimethylsilylamino)ferrocene (1) reacted with tBuPCl2 to form the first example of a [2]ferrocenophane ([2]FCP) bridged by nitrogen and phosphorus (2). Sulfurization of 2 followed by column chromatography on silica gel gave the expected [2]FCP with a tBu(S)PN(SiMe3) bridging moiety (3a) and its desilylated counterpart with a tBu(S)PNH bridging moiety (3b). The molecular structure of 3b was determined by single-crystal X-ray analysis (α = 18.40(11)°). Using a common synthetic methodology, two new 1-amino-1'-bromoferrocene derivatives were prepared, one species with a PhCH2 (6a) and another with a tBuCH2 group (6b) on nitrogen. Dilithiation of 6a followed by addition of tBuPCl2 gave a mixture of three constitutional isomers: the targeted [2]FCP (7a), the 1,1'-disubstituted ferrocene derivative (tBuPH)(PhCH═N)fc (8a), and the [3]FCP bridged by a (NH)(CHPh)PtBu moiety (9a). NMR spectroscopy revealed that 8a is the precursor for 9a. The salt-metathesis reaction of the dilithio derivative of 6b with tBuPCl2 exclusively gave the 1,1'-disubstituted ferrocene derivative (tBuPH)(tBuCH═N)fc (8b), which does not isomerize to the respective [3]FCP. DFT calculations at the M06/6-311+G(d,p) level were used to better rationalize these unexpected results.

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“…A broad variety of such polymers has been synthesized in laboratory. The bridge moiety can vary from group 13 (B, Al, Ga, In) [9][10][11][12] to group 14 (Si, Ge, Sn) [13][14][15][16][17] , group 15 (P, As) [18][19][20] , and group 16 elements (S, Se) 21,22 . The metallocene can cover almost the whole first-row transition metal series (Sc-Ni) and some second-and third-row transition metal species (Zr, Hf, Pt) [23][24][25][26][27] .…”

Section: Introductionmentioning

confidence: 99%

Silicon Bridge-Tuned Electronic Structures and Transport Properties of Polymetallocenes

PEI¹,

ZHANG²,

Shang³

et al. 2016

Acta Physico-Chimica Sinica

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Indium‐Bridged [1]Ferrocenophanes

Cited by 25 publications

References 108 publications

Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

[n]Ferrocenophanes (n = 2, 3) with Nitrogen and Phosphorus in Bridging Positions

Silicon Bridge-Tuned Electronic Structures and Transport Properties of Polymetallocenes

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