AD-AIIS 945 COLUMBIA UNIV N4EW YORK DEPT OF CHEMISTRY Ff B~fINDUCTION OF OLEFIN METATHESIS BY PHENYLACETYLENE PtLUS TUNGSTEN--CYCCU)JUN 82 T J KATZ, C HAN N00014-79-C-0663

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4. 'TITLE (d Sub"111e) S. Type DP REPORT & PZRIOD COVEREDTechnical Report, 8/1/79-

Induction of Olef in Metathesis by Phenylacetylene 6/21/82Plus Tungsten Hexachioride 4. PERFORMING ORG. REPORT NUM86ER

7. AU ?NBRMe 6. CONTRACT OR GRANT NUNbI9R1(e

Thomas J. Katz, Chien-Chung Han N00014-79-C-0683

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4ff Thomas 3. KatzDepartment of Chemistry, Columbia University NR 356-726

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To be published in Organometallics

DTICI1S1. IKY WORDS (Congiauo an reverse side it necesay -u idetitY by block ninabet)

C) Polymers Metathesis Alkenes ,JUN 2 3 1982C.) Polymerization Metal-carbenes AlkynesLAJ Catalysis Polyacetylenes 60

Initiation PolyalkenamersE

2& ASTRACT (ComeoAs ureverse side to n...esoy and Idmnily by block inumber)

Phenylacetylene induces tungsten hexachloride to initiate metatheses of cis-2-pentene, cyclopentene, cycloheptene, and cyclooctene. In too large amounts, how-ever, it i's ineffective. The reactions are run in the atmosphere. The stereo-selectivities for cis-olefins are moderate.

DD I 1473 EDITION OF I Nov 05 IS 0BSOLETE

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Task No. NR 356-726

TECHNICAL REPORT NO. 4

Induction of Olefin Metathesis by Phenylacetylene

Plus Tungsten Hexachloride

by

Thomas J. Katz, Chien-Chung Han

Prepared for Publication

in

Organometallics

Columbia UniversityDepartment of Chemistry

New York, New York

June 21, 1982

Reproduction in whole or in part is permitted forany purpose of the United States Government

This document has been approved for public releaseand sale; its distribution is unlimited

-2-

The discovery by Hasuda et al. that tungsten hexachloride initiates

polymerization of phenylatetylene1 suggests the following proposition:

that phenylacetylene may eifectively replace the highly reactive organo-

aluminum component in the mixture with tungsten hexachloride that is

the archetypical2 *and still standard initiator for olefin metathesis.3

For if the metal-catalyzed polymerization of acetylenes is an olefin

metathesis, 4- 6 a metallic compound that induces an acetylene to

polymerize should itself be induced by the acetylene to metathesize

olefins. The idea was demonstrated recently with phenylacetylene

plus (phenylmethoxycarbene)pentacarbonyltungsten.6 It is shown here

also for phenylacetylene plus tungsten hexachloride, a combination that

is more available, acts faster, induces fair stereoselectivy, and can be

used unprotected in the atmosphere.7

Fig I Figure 1 shows phenylacetylene's effect on the metathesis of

cis-2-pentene 14 according to eq 115 As phenylacetylene is added, the

CH3CHCHC2H5 + WCI 6 + C6H5CBCH200 :1I: x (1)

C6H5CI

C 6 H C o ( C H C H 4 3. + ( Y C2 H N V

amount of reaction, negligible in its absence, rises dramatically

and then falls. Complete reaction is easily achieved, but only when

the amount of acetylene is appropriate.

Table I Table I similarly shows phenylacetylene's ability to stimulate

tungsten hexachloride to polymerize three cyclic olefins (eq 2), reactions

that (as seen in the table) occur inavoreciably, if at all, when

.... ... • . " , "

-3-

100F

80

70

2Iu60-

502

0 40

30-

20-

10

1 2 3 4 5 6 7 8

200 X [c6H =CcH]/[WCI6]

Fu . The extent of reaction according to eq I as a function of x.

precent metathesis is recorded as 200r/(1 + 2r), where r is the ratio in

moles of either 2-butene to 2-pentene or 3-hexene to 2-pentene. The

bars span the two values associated with r measured in the two ways.

-4-

+' WCI 6 + P615 cM4 -(2)2 O I : X n

phenylacetylene is absent. That the polymers formed are indeed

polyalkenamers, not saturated vinyl polymers, is attested to by their

IH NHR spectra displaying only the required resonances and

intensities. The latter measure contamination by saturated hydrocarbon

amounting to no more than 4-9% (±4%).

Table II Table 1I shows that for cyclopentene, as for 2-pentene, while small

amounts of phenylacetylene induce metathesis, larger amounts quench

reaction. The decreased molecular weights (also recorded there) when the

amount of acetylene is large imply that growing chains rather than

initiating centers are being extinguished. This termination may involve

eq 3, the transformation of a simpler metal-carbene into one more highly66

substituted and with conjugating groups. One might speculate that

the initiation involves eq 4, possibly accompanied by

+ C 6 H 5 C=CM (3)

wc1 5wo 4 (4)

-CWC-+ WI6 - -C-CCl- - -C-CC 2-

,I

reaction with additional acetylene reducing the tungsten's oxidation

state.1 8

A hypothesis associating diminished stereoselectivity with the

presence of Lewis acids3e ,1 9 suggests that stereoselectivity should

increase when an aluminum halide is replaced by phenylacetylene and

decrease when (phenylmethoxycarbene) pentacarbonyltungsten is replaced

by tungsten hexachloride. The stereoselectivities recorded in Table II

and the stereochemistries of the 2-butenes (initially 69.6% cis) and

3-hexenes (initially ca. 54% cis) in Figure 1 accord with this hypothesis. 20

Acknowledments. We are grateful to the National Science Foundation

(CHE-81-08998) and the U.S. Office of Naval Research for support.

Referegnces and__Notes

(1) Masuda, T.; Hasegawa, K.; Higashimura, T. Macromolecules

1974, 7, 728.

(2) Natta, G.; Dall'Asta, G.; Mazzanti, G. Angew. Chem. Int. Ed.

Engl. 1964, 3, 723.

(3) (a) Banks, R.L. Catalysis (London) 1981, 4, 100. (b) Calderon,

N.; Lawrence, J. P.; Ofstead, E. Adv. Organomet. Chem. 1979, 17, 449.

(c) Grubbs, R. H. Prog. Inorg. Chem. 1978, 24, L. (d) Rooney, J. J.;

Stewart, A. Catalysis (London) 1977, 1, 277. (e) Katz, T. J. Adv.

Organomet. Chem. 1977, 16, 283. (f) Haines, R. J.; Leigh, G.J. Chem.

Soc. Rev. 975 , 1. (g) Mol, J. C.; Moulijn, J. A. Adv. Catal. 1975,

24, 131. (h) Dall'Asta, G. Rubber Chem. Techn. 1974, 47, 511.

(4) Masuda, T.; Sasaki, N.; Higashimura, T. Macromolecules 1975,

8, 717.

(5) Katz, T. J.; Lee, S. J. J. Am. Chem. Soc. 1980, 102, 422.

-6-

(6) (a) Katz, T. J. ; Lee, S. J. ; Nair, M.; Savage, E. B. Ibid.

U8 0, 102, 7940. (b) Katz, T. J.; Savage, E. B.; Lee, S. J.; Nair, M.

Ibid. U80102, 7942.

(7) Tungsten hexachloride alone does not metathesize olefins that

are unstrained,a but it does metathesize examples that are strained (like norbornene

and dicyclopentadiene).p Klpper demonstrated that combined with more

reactive olefins it would induce the reactions of those that are less

reactivel and Makovetsldi et al. very recently discovered results

similar to some of those reported here, in which it is effective in

12combination with acetylenes. Phenylacetylene is also recorded among

additives that enhance the reactivity of tungsten hexachloride

plus tetrabutyltin.13

(8) In the presence of oxygen, but not in its absence, WCI 6 is

reported to polymerize cyclopentene to polypentenamer. 9 Similar, but not

identical, experiments (see Table I) failed for us. After a long time

(22 h) at 30 OC with WC16 in air in the absence of solvent, cyclopentene

1gave a 2.6% yield of polymer that was 80% saturated ( H NMR analysis).

In an equal volume of chlorobenzene (not toluene and not distilled from

triethylaluminum) after the same amount of time it did not polymerize

appreciably.

(9) Amass, A.J.; McGourtey, T.A. Eur. Polym. j. 1980, 16, 235.

(10) Oshika, T.; Tabushi, H. Bull. Chem. Soc. Jpn. 1968, 41, 211.

(11) Kpper, F.-W. Ansew. Makromol. Chem. 9, 80, 207.

(12) Makovetskii, K. L.; Red'kina, L. I.; Oreshkin, I. A. Izv. Akad.

Nauk SSSR, Ser. Khim. 1981, 1928.

-7-

(13) Ichikava, K.; Watanabe, 0.; Takagi, T.; Fukuzumi, K. J. Cacal.

97 44, 416.

(14) 99.6% cis, containing 0.25% n-pentane.

(15) The volume of chlorobenzene equalled that of the cis-2-pentene.

No precaution was taken to exclude air.

(16) Katz, T. J.; Lee, S. J.; Acton, N. Tetrahedron Lett. 1976, 4247.

(17) The 13C NMR spectra of polyalkenamers are described in reference

14, in the references in its footnote 18, and in (a) Carmen, C. J.;

Wilkes, C.E. Macromolecules 1974, 7, 40. (b) Chen, H. Y. Appl. Polym.

Spectrosc. I 7.

(18) (a) Greco, A.; Pirinoli, F.; Dall'Asta, G. J. Organometal.

Chem. 1973, 60, 115. (b) San Fillipo, Jr., J.; Sowinski, A. F.; Romano,

L. J. 3. Am. Chem. Soc. 1974, 97, 1599.

(19) Katz, T. J.; Hersh, W. H. Tetrahedron Lett. 1977, 585.

(20) See the results and sumaries in references 3e, 6a, 16 , and 19.

KUpper's aluminum-free catalysts induce stereochemistries like those

here.11 For cyclopentene's metathesis decreasing amounts of aluminum

halides decrease the stereoselectivity, and metals (like S22 and Si )

whose halides are less acidic than aluminum's enhance stereoselectivity.

(21) (a) Ganther, P. et al. Angew. Makromol. Chem. 1971, 4, 87 and

16/17, 27. (b) tvin, K. J.; Laverty, D. T.; Rooney, J. J. Makromol.

Chem. "7,178 , 1543.

(22) Ivin, K. J.; Lapienis, G.; Rooney, J. J. Polymer 1980, 21, 367.

(23) Oreshkin, I. A. et al. Eur. Polm. J. 1 , 13, 447.

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