Living cyclopolymerization of 1,6-heptadiyne derivatives using well-defined alkylidene complexes. Polymerization mechanism, polymer structure, and polymer properties

Journal Article · Wed Apr 06 00:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00086a016· OSTI ID:7069646

Fox, H H; Wolf, M O; O'Dell, R; Lin, B L; Schrock, R R; Wrighton, M S ^[1]

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1. Massachusetts Inst. of Technology, Cambridge, MA (United States)

We report here the living cyclopolymerization of 1,6-heptadiyne derivatives (usually 4,4-disubstituted) using well-defined alkylidene complexes as initiators. Diethyl dipropargylmalonate (2a), di-tert-butyl dipropargylmalonate (2b), optically active di-(1R,2S,5R)-([minus])-menthyl dipropargylmalonate (2c([minus])), di-(1S,2R,5S)-(+)-menthyl dipropargylmalonate (2c(+)), di-(1R)-endo-(+)-fenchyl dipropargylmalonate (2d), 4,4-bis[[(p-tolylsulfonyl) oxy]methyl]-1,6-heptadiyne (3b), 4,4-bis[(trimethylsiloxy)methyl]-1,6-heptadiyne (3c), the cyclic silyl ether, PhEtSi(OCH[sub 2])[sub 2]C-(CH[sub 2]C[triple bond]CH)[sub 2] (3d), and N,N-dipropargyl-2,4,6-triisopropylbenzamide (5b) are polymerized to give soluble polymers in high yield using Mo(NAr)(CHCMe[sub 2]Ph)(OR[sub F6])[sub 2] (1a; Ar = 2,6-i-Pr[sub 2]C[sub 6]H[sub 3], OR[sub F6] = OCMe(CF[sub 3])[sub 2]) as the initiator in 1,2-dimethoxyethane (DME). The polymers show a high degree of conjugation ([lambda][sub max] > 500 nm) and have narrow molecular weight distributions. Poly(2a) is soluble in most organic solvents (THF, C[sub 6]H[sub 6], toluene, CH[sub 2]Cl[sub 2], CHCl[sub 3], DME, DMF, MeCN). The mechanism of the polymerization has been investigated by [sup 1]H NMR studies and by monomer, initiator, and solvent variations. Symmetric, diphenyl-capped polyenes, [open quotes]pull-pull[close quotes] polyenes containing p-cyanophenyl end groups, and [open quotes]push-push[close quotes] polyenes containing p-dimethylamino end groups have all been prepared. 93 refs., 12 figs., 11 tabs.

• DOE Contract Number: FG02-86ER13564
• OSTI ID: 7069646
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 116:7; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKYNES
POLYMERIZATION
ESTERS
ORGANIC POLYMERS
MOLECULAR STRUCTURE
SOLUBILITY
AROMATICS
ELECTROCHEMISTRY
ETHERS
EXPERIMENTAL DATA
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
SILICON COMPOUNDS
SOLVENTS
VOLTAMETRY
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
HYDROCARBONS
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
POLYMERS
RESONANCE
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400400 - Electrochemistry
400102 - Chemical & Spectral Procedures