Living Anionic Ring-Opening Polymerization of Silicon-Bridged [1]Ferrocenophanes: Synthesis and Characterization of Poly(ferrocenylsilane)-Polysiloxane Block Copolymers

Rulkens, Ron; Ni, Yizeng; Manners, Ian

doi:10.1021/ja00105a090

Cited by 156 publications

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“…More recently, we have demonstrated that living ROP can also be achieved in solution at room temperature in the presence of anionic initiators (6). This has provided access to poly(ferrocenylsi1anes) with controlled molecular weights as well as to block copolymers (7). In addition, random copolymers are accessible via thermal copolymerization of different monomers (8).…”

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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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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“…Living anionic ROP of sila[1]ferrocenophanes was developed in the mid 1990s, 44,45 and allows access to PFSs with molecular weight control and predetermined chain end function, provided that low levels of impurity are present. 45,46 For this reason, high purity monomer is required and this is generally achieved by multiple recrystallisation and sublimation steps to remove ring-opened or cyclic and linear oligomeric contaminants.…”

Section: Living Anionic Rop Involving Cleavage Of the Cp-si Bondmentioning

confidence: 99%

“…44,45 This allowed the preparation of well-defined materials with controlled molecular weights and narrow polydispersities (PDI < 1.2). The proposed mechanism involves nucleophilic attack of the initiator at the bridging silicon centre followed by Cp-Si cleavage to generate an anionic propagating site based on the iron-coordinated Cp ring.…”

Section: Living Anionic Rop Involving Cp-si Bond Cleavagementioning

confidence: 99%

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

Qiu

Winnik

et al. 2016

Macro Chemistry & Physics

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“…In the following years, the living anionic route [10,11] and transition metal-catalyzed route [12,13] were also established, which enable the organometallic polymers to have controllable structures.…”

Section: Synthesis Of Linear Ferrocene-based Polymersmentioning

confidence: 99%

Progress in the controllable synthesis of novel ferrocene-based polymers and their applications

Wang

et al. 2007

Designed Monomers and Polymers

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Living Anionic Ring-Opening Polymerization of Silicon-Bridged [1]Ferrocenophanes: Synthesis and Characterization of Poly(ferrocenylsilane)-Polysiloxane Block Copolymers

Cited by 156 publications

References 0 publications

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

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

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

Progress in the controllable synthesis of novel ferrocene-based polymers and their applications

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