Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials
- Patrycja Żak and
- Cezary Pietraszuk
Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28
Graphical Abstract
Figure 1: Cubic octasilsesquioxane.
Scheme 1: Reactivity of vinylsilanes in the presence of ruthenium alkylidene complexes; a) cross metathesis, ...
Figure 2: The scope and limitations of metathesis in transformations of vinyl-substituted siloxanes and silse...
Scheme 2: Application of olefin metathesis in the synthesis and modification of POSS-based materials: a) func...
Figure 3: Olefin metathesis catalysts used in transformations of silsesquioxanes.
Figure 4: Octavinyl-substituted cubic silsesquioxane (OVS) and spherosilicate.
Scheme 3: Cross metathesis of OVS with terminal olefins (stereoselectivity as discussed in the text).
Scheme 4: Cross metathesis of OVS with substituted styrenes.
Scheme 5: Modification of OVS via CM with styrenes.
Figure 5: Vinylbiphenyl chromophore-decorated cubic silsesquioxanes.
Scheme 6: Cross metathesis of OVS with carboranylstyrene.
Scheme 7: Synthesis of octakis[2-(p-carboxyphenyl)ethyl]silsesquioxane via CM and subsequent hydrogenation.
Scheme 8: Cross metathesis of monovinyl-POSS with olefins.
Scheme 9: Cross metathesis of monovinyl-POSS with highly π-conjugated substituted styrenes.
Scheme 10: Cross metathesis of monovinylgermasilsesquioxane with styrenes.
Scheme 11: Cross metathesis of DDSQ-2SiVi with olefins.
Scheme 12: Cross metathesis of DDSQ-2SiVi with substituted styrenes.
Scheme 13: Cross metathesis of (DDSQ-2GeVi) with olefins.
Scheme 14: CM of divinyl-substituted T10 and T12 with 4-bromostyrene (selected isomers are shown).
Scheme 15: Synthesis of vinylstilbene derivatives of T10 and T12 via a sequence of CM and Heck coupling.
Scheme 16: Cross metathesis of allyl-POSS with tert-butyl acrylate and (Z)-1,4-diacetoxy-but-2-ene.
Scheme 17: Cross metathesis of allyl-POSS with olefins.
Scheme 18: Acyclic diene metathesis copolymerization of DDSQ-2SiVi with diolefins.
Scheme 19: Acyclic diene metathesis copolymerization of DDSQ-2GeVi with diolefins.
Scheme 20: Ring-opening metathesis copolymerization of norbornenylethyl-POSS with norbornene.
Scheme 21: Synthesis of a polyethylene–POSS copolymer via ring-opening metathesis copolymerization of norborne...
Scheme 22: ROMP of norbornenylethyl-POSS with 1,5-cyclooctadiene.
Scheme 23: Copolymerization of POSS-functionalized norbornene with DCPD.
Scheme 24: Copolymerization of tris(norbornenylethyl)-POSS with DCPD.
Scheme 25: Copolymerization of N-(propyl-POSS)-7-oxanorbornene-5,6-dicarboximide with 3-(trifluoromethyl)pheny...
Figure 6: Homopolymers and copolymers having POSS groups attached to the main chain via flexible spacers of d...
Scheme 26: Ring-opening metathesis copolymerization of POSS-NBE with methyltetracyclododecene.
Scheme 27: Synthesis of block copolymer via ROMP by sequential monomer addition.
Scheme 28: Synthesis of a liquid crystalline polymer with POSS core in the side chain.
Scheme 29: Sequential synthesis of copolymers of polynorbornene containing POSS and PEO pendant groups.
Scheme 30: Synthesis of rodlike POSS−bottlebrush block copolymers [54].
Scheme 31: Surface-initiated ROMP producing copolymer layers on the surface of CdSe/ZnS quantum dots.
New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP
- Patrycja Żak,
- Szymon Rogalski,
- Mariusz Majchrzak,
- Maciej Kubicki and
- Cezary Pietraszuk
Beilstein J. Org. Chem. 2015, 11, 1910–1916, doi:10.3762/bjoc.11.206
Graphical Abstract
Figure 1: Coordination motif of latent catalyst of olefin metathesis in which alkylidene ligand is bound to t...
Figure 2: Known latent catalysts of olefin metathesis in which alkylidene ligands are bound to a heteroatom, ...
Figure 3: Selected, known aryloxybenzylidene chelates [9,10].
Scheme 1: Synthesis of catalyst precursors 4–6 [11].
Scheme 2: Synthesis of catalysts 8–10.
Scheme 3: Synthesis of catalysts 13 and 14.
Figure 4: ROMP of COD. Conditions: CH2Cl2, 40 °C, 0.5 M, [COD]:[Ru] = 20000; For clarity, only two representa...
Figure 5: ROMP of cod. Conditions: CH2Cl2, 40 °C, 0.5 M, [cod]:[Ru] = 20000; For clarity only representative ...
Scheme 4: ROMP of monomer 15.
Figure 6: ROMP of monomer 15. Conditions: CDCl3, 40 °C, 0.08 M, [15]:[Ru] = 200.
Figure 7: ROMP of monomer 15. Conditions: CDCl3, 23 °C, 0.08 M, [15]:[Ru] = 200.
Scheme 5: Formation of phosphine free dimeric complex in the presence of CuCl.
Figure 8: A perspective view of complex 16, the ellipsoids are drawn at the 50% probability level. Hydrogen a...
Scheme 6: Synthesis of complexes 1a and 8 starting from dimer 16.
Scheme 7: Activation of complex 8 with one equivalent of HCl.
