Studies on polyyne polymers containing transition metals in the main chain. VII. Synthesis and characterization of palladium‐polyyne polymers

Abstract

Metal‐polyyne polymers consisting of palladium and conjugated acetylenic systems, magnified image where PD and R represent the —Pd(PBu3)2—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω‐diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu3 (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R1 = R2 = H) having M̄w = 29,000 was obtained.

Synthesis and Characterization of Poly(aryleneethynylene)s and Their Corresponding Platinum-Linked Polymers

“…After metal incorporation the C≡C triple bond stretching frequency shifted from around 2200 cm -1 to lower wavelength at around 2100 cm -1 , which is the characteristics of Pt(II)-σ-acetylide compounds [31,32]. Another noticeable observation was strong (sp 3 H) -CH and (sp 2 H) =CH band peak in the organometallic compound which was absent in the corresponding organic polymer.…”

“…The rigid-rod Pt (II) acetylide polymer was prepared by two synthetic routes: a) by a dehydrohalogenation reaction [31] of diterminal arylethynylene with Pt (P n Bu 3 ) 2 Cl 2 in diethylamine using CuI as a catalyst and b) by reacting bis[(trimethylstannyl) ethynyl] pyridine with Pt(P n Bu 3 ) 2 Cl 2 in toluene containing a catalytic amount of CuI [32].…”

Unique Metal‐Diyne, ‐Enyne, and ‐Enediyne Complexes: Part of the Remarkably Diverse World of Metal‐Alkyne Chemistry

“…The same synthetic approach has been extended to the preparation of metal-diynyl complexes from across the periodic table (53). Rigid-rod s-alkynyl polymeric species (48,54) with M w > 10 6 (M w ¼ weight-average molecular weight) are also obtained from direct dehydrohalogenation (55,56), as well as alkyne ligand transfer (57), and O 2 -dependent coupling (58) strategies using cuprous halide and divalent, group 10 (VIII) metal halides. (c)Synthesis of the versatile group 14 (IV A) alkyne-transfer reagents (59)(60)(61) (e.g., Me 3 SnÀ ÀC À À À À À À CR from reaction of the alkyne with BuLi and Me 3 SnCl, and subsequent metathesis with transition metal chlorides yields the desired metal alkyne species with concomitant formation of the alkyl tin halide (62).…”

“…(54,192,272) The main chain of these polymers orients parallel or perpendicular ( Fig. 13) to the applied magnetic field of a simple nuclear magnetic resonance (NMR) magnet (56,273). Those polymers containing diethynyl aromatic bridges align parallel to the field while those with only dialkynyl units orient perpendicular to the external field due to the negative magnetic anisotropy of the alkyne units (273) interacts with materials possessing NLO properties, the electromagnetic wave of the incident radiation is perturbed producing phase, frequency, polarization, amplitude, and/or trajectory shifts of the transmitted radiation via harmonic generation, frequency mixing, and optical parametric oscillation.…”

Organometallic Polymers of the Transition Metals

“…[291][292][293][294] Continued interest in this class of polymer stems from the interesting optical properties that they possess. In the early 1990s, there were a number of reports on the synthesis of rigid-rod metal-containing polyynes by Lewis and coworkers using bis(trimethylstannylacetylides).…”