Synthesis and Structure of the First Sulfur‐Bridged [1]Ferrocenophane

Pudelski, John K.; Gates, Derek P.; Rulkens, Ron; Lough, Alan J.; Manners, Ian

doi:10.1002/anie.199515061

Cited by 72 publications

(33 citation statements)

References 29 publications

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“…[124] Sulfur-and selenium-bridged [1]ferrocenophanes 33 and 34 can be made by typical salt metathesis methods by using dilithiofer- rocene, given careful workup at low temperatures. [24,124] These tilted, strained species should exhibit interesting reactivity but, to date, this area has not been explored in detail.…”

Section: Group 16 Elements As Bridges Sulfur and Seleniummentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

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The structures, bonding, and ring-opening reactions of strained cyclic carbon-based molecules form a key component of standard textbooks. In contrast, the study of strained organometallic molecules containing transition metals is a much more recent development. A wealth of recent research has revealed fascinating nuances in terms of structure, bonding, and reactivity. Building on initial work on strained ferrocenophanes, a broad range of strained organometallic rings composed of a variety of different metals, pi-hydrocarbon ligands, and bridging elements has now been developed. Such strained species can potentially undergo ring-opening reactions to functionalize surfaces and ring-opening polymerization to form easily processed metallopolymers with properties determined by the presence of the metal and spacer. This Review summarizes the current state of knowledge on the preparation, structural characterization, electronic structure, and reactivity of strained organometallic rings with pi-hydrocarbon ligands and d-block metals.

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Section: Group 16 Elements As Bridges Sulfur and Seleniummentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

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“…We have also shown that ROP is catalyzed in solution by certain transition metal complexes (9) and that the ROP route can be extended to other strained [n]metallocenophanes; thus, polymers such as poly(ferrocenylgermanes) and poly(ferrocenylethy1enes) have been prepared from germanium-bridged [llferrocenophanes and hydrocarbon-bridged [2]ferrocenophanes, respectively (1& 17). Crystallographic studies have revealed that these polymerizable monomers possess ring-tilted structures in which the planes of the cyclopentadienyl ligands are tilted by angles of up to 3 1' (17). By contrast, in ferrocene the cyclopentadienyl rings are planar.…”

Section: [Traduit Par La Rbdaction]mentioning

confidence: 99%

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

Peckham¹,

Foucher²,

Lough³

et al. 1995

Can. J. Chem.

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The silicon-bridged [llferrocenophane Fe(q-C,H3SiMe,),(SiMe2) (5) was synthesized via the reaction of Li,[Fe(q-C,H,SiMe,),].tmeda (tmeda = tetramethylethylenediamine) with Me2SiC1, in hexanes. The disilane-bridged [2]ferrocenophane Fe(q-C5H3SiMe,),(Si2Me4) (7) was prepared using a similar route from the disilane C1Me2SiSiMe2C1. Despite the presence of sterically demanding SiMe, substituents on the cyclopentadienyl rings, compound 5 was found to undergo thermal ring-opening polymerization at 170°C to produce very soluble, high molecular weight poly(ferrocenylsi1ane) 6 with Mw = 1.4 x lo5, M , = 8.4 x lo4.However, the [2]ferrocenophane 7 was found to be resistant to thermal ring-opening polymerization even at 350°C and decomposed above 380°C. A single-crystal X-ray diffraction study of 7 revealed that the steric interactions between the bulky SiMe, groups are relieved by a significant twisting of the disilane bridge with respect to the plane defined by the centroids of the cyclopentadienyl ligands and the metal atom. The angle between the planes of the cyclopentadienyl rings in 7 was found to be 5.4(6)", slightly greater than that in the non-silylated analogue Fe(q-C5H4),(Si2Me4) (4a) (4.19(2)"), and dramatically less than the corresponding tilt angle of the strained, polymerizable, silicon-bridged ,(SiMe2) (1) (20.8(5)"). The length of the Si-Si bond in 7 (2.342(3) A) was found to be close to the sum of the covalent radii (2.34 A). Crystals of 7 are monoclinic, space group C'lc, with a = 23.689(3) A, b = 11.174(1) A, c = 31.027(3) A, p = 109.16(1)", V = 7758(2) A3, and Z = 12.Key words: ring-opening polymerization, ferrocenophane, organometallic polymers.Rksumk : On a synthCtist le [I]ferroctnophane pontC par un silicium, Fe(q-C5H3SiMe3),(SiMe2) (5), par une rkaction du Li,[Fe(q-C5H3SiMe3),].tmeda (tmeda = tCtramtthyltthylknediamine) avec du Me2SiC12 dans de l'hexane. On a prCparC le [2]ferroctnophane pontt par deux silanes, Fe(q-C5H3SiMe3),(Si2Me4) (7). faisant appel ti une voie sernblable i partir du disilane C1Me2SiSiMe2C1. MalgrC la prksence sur les noyaux cyclopentadiCnyles de substituants SiMe, ayant une demande stCrique irnportante, on a trouvC que le compose 5 subit une polymCrisation therrnique par ouverture de cycle 2 170°C qui conduit au poly(ferrocCnylsi1ane) 6 trks soluble et de poids rnolCculaire ClevC avec Mw = 1,4 x lo5, M,, = 8,4 x lo4. Toutefois, on a trouvC que le[2]ferrocCnophane 7 est resistant une polyrnCrisation therrnique par ouverture de cycle, rn&rne a 350°C, et qu'il se dCcornpose i 380°C. Une ttude de diffraction des rayons X par un cristal unique du composC 7 rnontre que les interactions stCriques entre les groupes SiMe, sttriquernent encombrants sont apaisCes par une dtforrnation irnportante du pont disilane par rapport au plan dtfini par les centro~des des coordinats cyclopentadienyles et de l'atome de metal. On a trouvC que l'angle entre les plans des noyaux cyclopentadienyles du composC 7 est de 5,4(6)", ce qui est 1Cgkrernent supCrieur $ i la valeur de 4,19(2)" observke...

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“…4 Characterization of the purple compound (3) by ! H NMR revealed a characteristic large separation between the a and (3 cyclopentadienyl protons (AS = 0.65 ppm).…”

Section: Chalcogen Bridged Rilferrocenophanesmentioning

confidence: 99%

Highly Strained Metallocenophanes: Synthesis and Ring-Opening of Sulfur-, Selenium- and Boron- Bridged [1]Ferrocenophanes

Gates

Rulkens

Dirk

et al. 1997

Phosphorus, Sulfur, and Silicon and the Related Elements

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Synthesis and Structure of the First Sulfur‐Bridged [1]Ferrocenophane

Cited by 72 publications

References 29 publications

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

Highly Strained Metallocenophanes: Synthesis and Ring-Opening of Sulfur-, Selenium- and Boron- Bridged [1]Ferrocenophanes

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