Isolation and characterisation of a well defined precatalyst for the ring-opening polymerisation of silicon-bridged [1]ferrocenophanes

Sheridan, John B.; Temple, Karen; Lough, Alan J.; Manners, Ian

doi:10.1039/a608466d

Cited by 50 publications

(45 citation statements)

References 19 publications

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“…[87] Transition-metal-catalyzed ROP was initially believed to proceed through homogeneous reactions. [89] Subsequent studies suggested a heterogeneous catalytic route with colloidal metal as the main active catalyst (Scheme 8). [90] The generated platinasila[2]ferrocenophane acts as a precatalyst.…”

Section: Polyferrocenylsilanesmentioning

confidence: 99%

Polyferrocenylsilane‐Based Polymer Systems

Bellas¹,

Rehahn²

2007

Angew Chem Int Ed

290

207

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The study of metallopolymers has blossomed into a mature field over the last few decades. Especially, polyferrocenylsilane (PFS) chemistry has taken a tremendous leap and continues to raise intense interest. Since the discovery of thermal ring-opening polymerization (ROP) of sila[1]ferrocenophanes, PFSs have been also accessed by anionic, cationic, transition-metal-catalyzed, and photolytic anionic ROP methodologies. A plethora of synthetic strategies have been devised, enabling access to a wide variety of copolymers, polyelectrolytes, and nanostructured materials. The distinctive physical properties and functions of many PFS-based polymers have been explored, leading to their apt exploitation in technical applications. Therefore, it is conceivable that PFS-related platforms might be indispensable nano-objects in the near future, as they stand on the verge of a new generation of sophisticated materials.

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Section: Polyferrocenylsilanesmentioning

confidence: 99%

Polyferrocenylsilane‐Based Polymer Systems

Bellas¹,

Rehahn²

2007

Angew Chem Int Ed

290

207

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“…When 7 a was treated with a stoichiometric amount of Pt(1,5-cod) 2 (cod cyclooctadiene), which has recently been found to insert in the SiÀipso-C bond of 1 (E SiMe 2 ) to form a 1-sila-2-platina[2]-ferrocenophane, [42] slow conversion (over 2 h) led to the formation of the platinum ± tin-bridged [2]ferrocenophane 9 (Scheme 2). [43] The insertion product 9 was characterized by Scheme 2.…”

mentioning

confidence: 99%

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

et al. 1998

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Abstract:The first examples of tinbridged [1]ferrocenophanes, Fe(h-C 5 H 4 ) 2 -SntBu 2 (7a) and Fe(h-C 5 H 4 ) 2 SnMes 2 (7b) have been synthesized by the low-temperature reaction of Fe(h-C 5 H 4 Li) 2´n TME-DA (TMEDA N,N,N',N'-tetramethylethylenediamine) with tBu 2 SnCl 2 and Mes 2 SnCl 2 (Mes 2,4,6-trimethylphenyl), respectively. They were isolated in 65 % (7a) and 85% (7b) yield as orange crystalline solids, which were characterized by multinuclear NMR and UV/Vis spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. The tilt angles between the planes of the cyclopentadienyl rings are 14.1(2)8 for 7a and 15.2(2)8 (average) for the three independent molecules of 7b in the unit cell. Although they have significantly smaller tilt angles than analogous [1]ferrocenophanes with the lighter Group 14 elements silicon or germanium in the bridge, 7 a and 7 b still readily undergo ring-opening polymerization (ROP) by thermal reaction in the solid state (7 a at 150 8C; 7 b at 180 8C), to give highmolecular-weight poly(ferrocenylstannane)s [Fe(h-C 5 H 4 ) 2 SntBu 2 ] n (8 a) and [Fe(h-C 5 H 4 ) 2 SnMes 2 ] n (8 b). Remarkably, 7 a and 7 b were also found to polymerize in solution at room temperature in the absence of externally added initiators. ROP is much more rapid for 7 a than for 7 b in solution. The cyclic dimers [Fe(h-C 5 H 4 ) 2 SnR 2 ] 2 (3; R tBu, Mes) were formed as by-products in amounts which depended on the solvent. Electrochemical studies of the cyclic dimers and polymers indicated the presence of significant Fe´´´Fe interactions that are mediated by the tin-atom spacer. When benzene solutions of 7 a and 7 b were treated with small amounts of Karstedts catalyst, slower polymerization was observed. Stoichiometric reaction of Pt(1,5-cod) 2 (cod cyclooctadiene) with 7 a yielded the novel trimetallic 1-stanna-2-platina[2]ferrocenophane Fe(h-C 5 H 4 ) 2 Pt(1,5-cod)SntBu 2 (9), which functioned as a sluggish catalyst for the ROP of 7 a and 7 b.

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“…Such insertions are well established for silacyclobutanes [3d] and related cyclic silaferrocenophanes [11]. Obviously, 2 cannot undergo such insertion and we propose that 3 either does not react or undergoes a reversible insertion without loss of phenol or formation of polymer.…”

Section: Mechanistic Interpretationmentioning

confidence: 91%

“…Protons H 11,13 and H 12 were observed at d 0.49-0.70 and d 1.23-1.48, respectively. The 13 C NMR spectrum showed C 12 at d 16.…”

Section: Mechanistic Interpretationmentioning

confidence: 95%

A planar silacyclobutane, 1,1-(rac-1,1′-bi-2-naphthoxy)-1-silacyclobutane and its unusual reaction with bis(1,5-cyclooctadiene)platinum(0)

Jain

Brunskill

Sheridan

et al. 2005

Journal of Organometallic Chemistry

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Isolation and characterisation of a well defined precatalyst for the ring-opening polymerisation of silicon-bridged [1]ferrocenophanes

Cited by 50 publications

References 19 publications

Polyferrocenylsilane‐Based Polymer Systems

Polyferrocenylsilane‐Based Polymer Systems

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

A planar silacyclobutane, 1,1-(rac-1,1′-bi-2-naphthoxy)-1-silacyclobutane and its unusual reaction with bis(1,5-cyclooctadiene)platinum(0)

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