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), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:7; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

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