Metal-Catalyzed Dehydropolymerization of Secondary Stannanes to High Molecular Weight Polystannanes

Imori, Toru; Lu, Victor; Cai, Hui; Tilley, T. Don

doi:10.1021/ja00145a001

Cited by 197 publications

(247 citation statements)

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“…[1][2][3][4][5][6][7][8][9][10] These polymers, which typically are of the composition (-SnR 2 -) n and termed polystannanes, are structurally related to corresponding polymers with the semi-metals silicon or germanium (i.e., elements that are located in the periodic table in the same group as tin) and are of potential interest as semiconductors. [11][12][13] However, the synthesis of linear polystannanes in high yield and free of cyclic oligomers has been achieved only recently [2,3] and, therefore, until now the properties of polystannanes have been relatively little explored.…”

Section: Introductionmentioning

confidence: 99%

Oriented Poly(dialkylstannane)s

Choffat

Fornera

Smith

et al. 2008

Adv Funct Materials

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The inorganic (or ‘organometallic’) polymers poly(dibutylstannane), poly(dioctylstannane), and poly(didodecylstannane) have been oriented by shear forces, the tensile drawing of blends with polyethylene, and deposition from solution onto glass slides coated with an oriented, friction‐deposited poly(tetrafluoroethylene) (PTFE) layer. Orientation of the polystannanes has been examined by polarization microscopy, UV‐vis spectroscopy with polarized light, and X‐ray diffraction and their direction is found to depend on the length of the alkyl side groups and the method of orientation. Remarkably, in some cases the polystannane backbones are oriented parallel and in other instances perpendicular to the direction of the external orientation stimuli. The latter structural arrangement is most conspicuous for polymers substituted with dodecyl side groups, which are found to align parallel to the applied orientation direction, which forces the polymer backbone into a perpendicular position. Finally, UV‐vis spectra indicate that changes in the backbone conformation of certain polystannanes might be induced by applying mechanical stress.

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Section: Introductionmentioning

confidence: 99%

Oriented Poly(dialkylstannane)s

Choffat

Fornera

Smith

et al. 2008

Adv Funct Materials

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“…However, examples of the use of transition metal catalyzed dehydrocoupling reactions for the preparation of a variety of homo-and heteronuclear bonds between main group elements have been demonstrated beginning with the use of titanocene complexes to convert primary silanes to polysilanes in 1986. [4] New classes of inorganic macromolecules such as polystannanes [5] have been generated via catalytic dehydrocoupling methods while several examples of PÀP, [6] BÀSi, [7] SnÀTe, [8] SiÀP, [9] SiÀN [10] and SiÀO [11] bond-forming reactions have also been reported. [12] As part of our continuing program to develop novel extended structures based on main group elements, [13] we have studied the late transition metal (e.g.…”

Section: Introductionmentioning

confidence: 99%

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

Clark

Rodezno

Clendenning

et al. 2005

Chemistry A European J

118

112

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The dehydrocoupling of the fluorinated secondary phosphine-borane adduct R2PH.BH3 (R = p-CF3C6H4) at 60 degrees C is catalyzed by the rhodium complex [{Rh(mu-Cl)(1,5-cod)}2] to give the four-membered chain R2PH-BH2-R2P-BH3. A mixture of the cyclic trimer [R2P-BH2]3 and tetramer [R2P-BH2]4 was obtained from the same reaction at a more elevated temperature of 100 degrees C. The analogous rhodium-catalyzed dehydrocoupling of the primary phosphine-borane adduct RPH2.BH3 at 60 degrees C gave the high molecular weight polyphosphinoborane polymer [RPH-BH2]n (Mw = 56,170, PDI = 1.67). The molecular weight was investigated by gel permeation chromatography and the compound characterized by multinuclear NMR spectroscopy. Interestingly, the electron-withdrawing fluorinated aryl substituents have an important influence on the reactivity as the dehydrocoupling process occurred efficiently at the mildest temperatures observed for phosphine-borane adducts to date. Thin films of polymeric [RPH-BH2]n (R = p-CF3C6H4) have also been shown to function as effective negative-tone resists towards electron beam (e-beam) lithography (EBL). The resultant patterned bars were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

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“…in the range convenient for polystannanes. [16,34] UV-vis absorption spectra reveal that phenyl groups induce a bathochromic shift of the wavelength at maximum absorbance (Table 3 and Fig. 5), which might be associated with increasing delocalization of electrons with increasing number of aromatic groups in the polymer.…”

Section: Uv-vis Spectra and Dichroic Ratio After Shearingmentioning

confidence: 99%

From poly(dialkylstannane)s to poly(diarylstannane)s: comparison of synthesis methods and resulting polymers

Lechner

Trummer

Bräunlich

et al. 2011

Applied Organom Chemis

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The efficiency and applicability of three different methods to synthesize polystannanes with different side chains are described. By means of dehydrogenative coupling utilizing the transition metal catalyst RhCl(PPh 3 ) 3 (Wilkinson's catalyst), n-Bu 2 SnH 2 reached the highest molar masses. Dehydrogenetive coupling in the presence of tetramethylethylenediamine could be best employed for (4-n-BuPh) 2 SnH 2 . Wurtz coupling using sodium in liquid ammonia was best suited for Ph 2 SnCl 2 . Next to the above-mentioned educts, n-Bu(Ph)SnX 2 (X = H or Cl (as appropriate for the particular route) was used for polymerization resulting in one of so far rare example of asymmetric polystannanes with high molecular masses.

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Metal-Catalyzed Dehydropolymerization of Secondary Stannanes to High Molecular Weight Polystannanes

Cited by 197 publications

References 1 publication

Oriented Poly(dialkylstannane)s

Oriented Poly(dialkylstannane)s

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

From poly(dialkylstannane)s to poly(diarylstannane)s: comparison of synthesis methods and resulting polymers

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