METAL COMPLEXES AND A PROCESS OF PREPARING THEM

Abstract

A compound of the formula II (I) in which X is substituted pyrrolide with the general structure of (II) in which R.sup.a-R.sup.d are independently selected from H, C1-C4 alkyl, C1-C4 alkoxy, aryl, aryloxy, dialkylamino, diarylamino, halogen, trifluoromethyl, cyano, nitro, sulfonyl and sulfinyl. Y is C1-C6 alkoxy, C1-C10 aryloxy, optionally substituted; R.sup.1 is selected from H, C1-C12 alkyl and 5- to 18-membered aryl, optionally substituted; R.sup.2 is selected from C1-C12-alkyl, 5- to 18-membered aryl, optionally substituted; R.sup.3 is selected from C1-C12 alkyl, 5- to 18-membered aryl, optionally substituted; and 15 12.sup.4-R11 are independently selected from H, C1-C4 alkyl and halogen. The compounds are particularly effective precursors of metathesis catalysts for the polymerisation of dicyclopentadiene.

##STR00001##

Claims

1. A compound of the formula II ##STR00009## in which X is substituted pyrrolide with the general structure of ##STR00010## in which R.sup.a-R.sup.d are independently selected from H, C1-C4 alkyl, C1-C4 alkoxy, aryl, aryloxy, dialkylamino, diarylamino, halogen, trifluoromethyl, cyano, nitro, sulfonyl and sulfinyl; Y is selected from C1-C6 alkoxy and C1-C10 aryloxy, both of which may be substituted with alkoxy, aryloxy, dialkylamino, diarylamino, halogen, trifluoromethyl, cyano, nitro, sulfonyl and sulfinyl R.sup.1 is selected from H, C1-C12 alkyl and 5- to 18-membered aryl, both of which may be substituted with one or more of C1-C12-alkyl, 5- to 18-membered aryl, C1-C12-alkyloxy, di-(C1-C4-alkyl)amino, halogen, trifluoromethyl, cyano and nitro residues; R.sup.2 is selected from C1-C12-alkyl and 5- to 18-membered aryl, both of which may be substituted with one or more of C1-C12 alkyl, 5- to 18-membered aryl, C1-C12-alkyloxy, di(C1-C4alkyl)amino, halogen, trifluoromethyl, cyano, nitro residues; R.sup.3 is selected from C1-C12 alkyl and 5- to 18-membered aryl, both of which may be substituted with one or more of C1-C12 alkyl, 5- to 18-membered aryl, C1-C12-alkoxy, di(C1-C4-alkyl)amino, halogen, trifluoromethyl, cyano and nitro residues; and, R.sup.4-R.sup.11 are independently selected from H, C1-C4 alkyl and halogen.

2. A compound according to claim 1, in which: in X, R.sup.b and R.sup.c are H, and R.sup.a and R.sup.d are independently selected from H, methyl and phenyl; R.sup.1 and R.sup.2 are selected from H, C1-C5 alkyl and 5- to 10-membered aryl, which may be substituted with one or more of C1-C4-alkyl, halogen and trifluoromethyl, with the proviso that only one of R.sup.1 and R.sup.2 can be H; R.sup.3 is selected from C1-C5 alkyl and 5- to 10-membered aryl, both of which may be substituted with one or more of C1-C4 alkyl, 5- to 10-membered aryl and C1-C4-alkoxy; and R.sup.4-R.sup.11 are independently selected from H, C1-C4 alkyl and halogen.

3. A compound according to claim 2, in which in X, R.sup.b and R.sup.c are H, and R.sup.a and R.sup.d are both methyl or both phenyl; R.sup.1 and R.sup.2 are selected such that one of them is H and the other is selected from C1-C5 alkyl and 5- to 10-membered aryl, which may be substituted with one or more of C1-C4-alkyl, halogen and trifluoromethyl; R.sup.3 is selected from C1-C5 alkyl and 5- to 10-membered aryl, which may be substituted with one or more of C1-C4 alkyl, 5- to 10-membered aryl, C1-C4-alkoxy, halogen, and trifluoromethyl; R.sup.4-R.sup.11 are hydrogen.

4. A compound according to claim 1, selected from compounds of the Formulae III-VI: ##STR00011##

5. A compound according to claim 1, selected from the compounds of the Formulae III-V: ##STR00012##

6. Use of a compound according to claim 1 in the preparation of a polymer of dicyclopentadiene.

Description

Example 1

Preparation of the Compound of Formula III

[0041] The bispyrrolide precursor W(CHCMe.sub.2Ph)(NAr.sup.diMe)(Me.sub.2Pyr).sub.2 (Ar.sup.diMe=2,6-dimethylphenyl, Me.sub.2Pyr=2,5-dimethylpyrrolide) (312 mg, 0.5 mmol) was dissolved in benzene (5 mL). Ph(CF.sub.3).sub.2COH (84 microL, 0.5 mmol) was added, and the reaction mixture was stirred for 30 min at room temperature. An aliquot of the reaction mixture was analyzed by .sup.1H NMR and .sup.19F NMR to confirm the formation of the MAP complex. 1,10-Phenantroline (90 mg, 0.5 mmol) was added. The reaction mixture was stirred for an hour at room temperature, and then it was moved into the freezer. Next morning the reaction mixture was thawed, yielding part of the product as orange crystals. Precipitation of the product was completed by slow, gradual addition of pentane (10 mL in total). The reaction mixture and a glass filter were cooled in the freezer, and the product was isolated by rapid filtration. It was washed with pentane on the frit, and dried in N.sub.2 stream. Orange solid. Isolated yield: 480 mg (quantitative).

[0042] .sup.1H-NMR (C.sub.6D.sub.6): 0.72 (s, 3H, NAr CH.sub.3), 1.77 (s, 3H, CH.sub.3 neophylidene), 1.99 (s, 3H, CH.sub.3 neophylidene), 2.44 (s, 3H, CH.sub.3 2,5-dimethylpyrrole), 2.53 (s, 3H, NAr CH.sub.3), 2.67 (s, 3H, CH.sub.3 2,5-dimethylpyrrole), 6.45 (d, .sup.3J.sub.HH=7.5 Hz 1H, NAr C.sub.meta-H), 6.54 (dd, .sup.3J.sub.HH=8.1, 5.0 Hz, 1H, H8-phen), 6.61 (t, .sup.3J.sub.HH=7.5 Hz, 1H, NAr C.sub.para-H), 6.65 (d, 1H, CH 2,5-dimethylpyrrole),), 6.67 (dd, .sup.3J.sub.HH=8.1, 5.2 Hz, 1H, H3-phen), 6.77 (d, 1H, CH 2,5-dimethylpyrrole), 6.93 (d,.sup.3J.sub.HH=7.5 Hz 1H, NAr C.sub.meta-H), 6.99 (d, 1H, H5-phen), 7.00 (d, 1H, H6-phen), 7.15 (m, 2H, neophylidene Ph C.sub.para-H, (C.sub.6F.sub.5).sub.2CH.sub.3CO C.sub.para-H), 7.17 (m, 1H, H7-phen) 7.29 (m, 4H, neophylidene Ph C.sub.meta-H, (C.sub.6F.sub.5).sub.2CH.sub.3CO C.sub.meta-H), 7.36 (m, 1H, H4-phen), 7.70 (m, 4H, neophylidene Ph C.sub.orto-H, (C.sub.6F.sub.5).sub.2CH.sub.3C.sub.orto-H), 8.77 (d, .sup.3J.sub.HH=5.0 Hz, 1H, H2-phen), 9.61 (dd, .sup.3J.sub.HH=5.2 Hz, .sup.4J.sub.HH=1.5 Hz, 1H, H9-phen), 11.99 ppm (s, 1H, W=CH,.sup.2J.sub.WH=10.0 Hz). [0043] .sup.19F-NMR (C.sub.6D.sub.6): 72.9 (q), 74.6 ppm (q). [0044] .sup.13C{.sup.1H}-NMR (C.sub.6D.sub.6): 17.6 (NAr CH.sub.3), 18.3 (NAr CH.sub.3), 20.2 (CH.sub.3 2,5-dimethylpyrrole), 30.1 (CH.sub.3 neophylidene), 34.8 (CH.sub.3 neophylidene), 108.6 (CH 2,5-dimethylpyrrole), 109.9 (CH 2,5-dimethylpyrrole), 123.7 (C3-phen), 124.0 (C8-phen), 124.1 (NAr C.sub.para), 125.2 (C6-phen), 126.4 (NAr C.sub.meta), 128.7 (NAr C.sub.meta) 137.0 (C7-phen), 138.1 (C4-phen), 152.7 (C2-phen), 160.0 ppm (C9-phen).

Example 2

Preparation of the Compound of Formula IV

[0045] The bispyrrolide precursor W(CHCMe.sub.2Ph)(NAr.sup.diiPr)(Me.sub.2Pyr).sub.2 (Ar.sup.diiPr=2,6-diisopropylphenyl, Me.sub.2Pyr=2,5-dimethylpyrrolide) (680 mg, 1 mmol) was dissolved in benzene (10 mL). Ph(CF.sub.3).sub.2COH (170 microL, 1 mmol) was added, and the reaction mixture was stirred for an hour at room temperature. An aliquot of the reaction mixture was analyzed by .sup.1H and .sup.19F NMR, which confirmed the formation of the MAP complex. 1,10-Phenantroline (180 mg, 1 mmol) was added. The reaction mixture was stirred for an hour at room temperature. An aliquot was analyzed by .sup.1H and .sup.19F NMR. Both methods confirmed the formation of one single stereoisomer of the target compound. The compound was spectroscopically pure. The solution of the complex was concentrated to ca. 3-4 mL. Pentane was added to room temperature. Precipitation of the target compound started after adding ca. 15 mL pentane. Some more pentane (ca. 10 mL) was added to complete precipitation. The mixture was stirred for an hour. The solids were isolated by filtration, washed with pentane, and dried first in N.sub.2 stream, and then in vacuum. Ocher solid. Yield: 936 mg (93%). The product was prepared from the isolated MAP complex, too, with similar yields.

[0046] .sup.1H-NMR (C.sub.6D.sub.6): 0.20 (d, .sup.3J.sub.HH=6.9 Hz, 6H, CH.sub.3CHCH.sub.3), 0.12 (d, .sup.3J.sub.HH=6.9 Hz, 6H, CH.sub.3CHCH.sub.3), 1.22 (d, .sup.3J.sub.HH=6.7 Hz, 6H, CH.sub.3CHCH.sub.3), 1.41 (d, .sup.3J.sub.HH=6.7 Hz, 6H, CH.sub.3CHCH.sub.3), 1.89 (s, 3H, CH.sub.3 neophylidene), 2.20 (sept, .sup.3J.sub.HH=6.9 Hz, 1H, CH.sub.3CHCH.sub.3), 2.24 (s, 3H, CH.sub.3 neophylidene), 2.36 (s, 3H, CH.sub.3 2,5-dimethylpyrrole), 2.74 (s, 3H, CH.sub.3 2,5-dimethylpyrrole), 4.25 (sept, .sup.3J.sub.HH=6.7 Hz, 1H, CH.sub.3CHCH.sub.3), 6.51 (dd, .sup.3J.sub.HH=8.1, 5.0 Hz, 1H, H8-phen), 6.63 (d, .sup.3J.sub.HH=2.7 Hz, 1H, CH 2,5-dimethylpyrrole), 6.63 (dd, .sup.3J.sub.HH=8.1, 5.2 Hz, 1H, H3-phen), 6.65 (d, .sup.3J.sub.HH=7.7 Hz 1H, NAr C.sub.meta-H), 6.69 (d, .sup.3J.sub.HH=2.7 Hz, 1H, CH 2,5-dimethylpyrrole),), 6.82 (t, .sup.3J.sub.HH=7.7 Hz, 1H, NAr C.sub.para-H), 7.00 (ABd, 2H, H5-phen, H6-phen), 7.14-7.20 (m, 2H, neophylidene Ph C.sub.para-H, OCPh(CF.sub.3).sub.2 C.sub.para-H), 7.15 (d, .sup.3J.sub.HH=7.7 Hz 1H, NAr C.sub.meta-H), 7.17 (m, 1H, H7-phen), 7.29 (m, 2H, OCPh(CF.sub.3).sub.2 C.sub.meta-H), 7.34 (m, 1H, H4-phen), 7.37 (m, 2H, neophylidene Ph C.sub.meta-H), 7.60 (m, 2H, OCPh(CF.sub.3).sub.2 C.sub.orto-H), 7.81 (m, 4H, neophylidene Ph C.sub.orto-H), 9.04 (d br, .sup.3J.sub.HH=5.1 Hz, 1H, H2-phen), 9.71 (dd, .sup.3J.sub.HH=5.0 Hz, .sup.4J.sub.HH=1.2 Hz, 1H, H9-phen), 12.20 ppm (s, 1H, W=CH, .sup.2J.sub.WH=9.5 Hz). [0047] .sup.19F NMR (C.sub.6D.sub.6): 69.1 (q), 76.3 ppm (q br).

Example 3

Preparation of the Compound of Formula V

[0048] The bispyrrolide precursor W(CHCMe.sub.2Ph)(NAr.sup.diMe)(Me.sub.2Pyr).sub.2 (Ar.sup.diMe=2,6-dimethylphenyl, Me.sub.2Pyr=2,5-dimethylpyrrolide) (156 mg, 0.25 mmol) was dissolved in toluene (10 mL). The solution was cooled to 38 Celsius in the freezer of the glove box. The solution was moved out of the glove box, and (CF.sub.3).sub.3COH (35 microL, 0.25 mmol) was added immediately at intensive stirring. The reaction mixture was allowed to warm to room temperature, and and it was left stirring overnight. An aliquot of the reaction mixture was analyzed by .sup.1H and .sup.19F NMR. The analysis confirmed the formation of the MAP complex, and also revealed the formation of a small amount of bisalkoxide (ca. 5 mol %). 1,10-phenantroline (45 mg, 0.25 mmol was added. The reaction mixture turned brownish red immediately. Phenantroline residues were washed into the reaction mixture with toluene (1 mL). The reaction mixture was stirred for an hour. An aliquot of the reaction mixture was analyzed by .sup.1H and .sup.19F NMR. The analysis confirmed the formation of the phenantroline adduct of the MAP complex, and also revealed the formation of a small amount of the phenantroline adduct of the bisalkoxide (ca. 5 mol %). The reaction mixture was concentrated to 1-2 mL, and precipitation of the product was initiated by the slow addition of pentane (ca. 10 mL). The mixture was stirred for an hour at room temperature to triturate the product, and then the reaction mixture was moved into the freezer to complete the precipitation of the target compound. The product was isolated by filtration, and dried on the frit in N.sub.2 stream. Red solid. Yield: 200 mg (85%). Purity>95%.

[0049] .sup.1H-NMR (C.sub.6D.sub.6) (ppm): 0.62 (s, 3H, CH.sub.3), 1.82 (s, 3H, CH.sub.3), 1.95 (s, 3H, CH.sub.3), 2.19 (s, 3H, CH.sub.3), 2.47 (s, 3H, CH.sub.3), 3.16 (s, 3H, CH.sub.3), 6.38-7.35 (m, 14H, aromatic), 7.69 (m, 2H, C.sub.ortho-H neophylidene), 8.60 (dd, J=5.2, 1.4 Hz, 1H, H2 Phen), 9.32 (d br, J=5.0 Hz, 1H, H2 Phen), 12.04 (s, .sup.2J.sub.WH=10.9 Hz, 1H, W=CH).

[0050] .sup.19F-NMR (C.sub.6D.sub.6) (ppm): 72.9 (s).

Example 4

Preparation of the Compound of Formula VI

[0051] The compound of Formula VI was prepared from W(CHCMe.sub.2Ph)(NAr.sup.diMe) (Me.sub.2Pyr).sub.2 (Ar.sup.diMe=2,6-dimethylphenyl, Me.sub.2Pyr=2,5-dimethylpyrrolide) and (CCl.sub.3)(CF.sub.3).sub.2COH by the method of Example 3. Yield 83%.

[0052] .sup.1H-NMR (C.sub.6D.sub.6): 0.56 (s, 3H, NAr CH.sub.3), 1.81 (s, 3H, CH.sub.3 neophylidene), 1.93 (s, 3H, CH.sub.3 neophylidene), 2.17(s, 3H, CH.sub.3 Me.sub.2Pyr), 2.43 (s, 3H, NAr CH.sub.3), 3.17 (s, 3H, CH.sub.3 Me.sub.2Pyr), 6.40 (d br, .sup.3J.sub.HH=7.3 Hz, 1H, NAr C.sub.meta-H), 6.58 (m, 2H, H3-phen, NAr C.sub.para-H), 6.63 (m, 1H, CH Me.sub.2Pyr), 6.66 (m, 1H, CH Me.sub.2Pyr), 6.65 (m, 1H, H3-phen), 6.86 (d br,.sup.3J.sub.HH=7.6 Hz, 1H, NAr C.sub.meta-H), 6.97 (ABq, 2H, H5-phen, H5-phen), 7.13 (m, 1H, neophylidene Ph C.sub.para-H), 7.16 (m, 1H, H4-phen), 7.31 (m, 3H, neophylidene Ph C.sub.meta-H, H4-phen), 7.68 (m, 2H, neophylidene Ph C.sub.orto-H), 8.57 (dd, J.sub.HH=5.2, 1.1 Hz, 1H, H2-phen), 9.52 (d br, J.sub.HH=4.8 Hz, 1H, H2-phen), 12.34 ppm (s, 1H, W=CH, .sup.2J.sub.WH=12.0 Hz).

[0053] .sup.19F-NMR (C.sub.6D.sub.6): 65.2 (q, .sup.4J.sub.FF=10.5 Hz), 68.0(q, .sup.4J.sub.FF=10.5 Hz).

[0054] .sup.13C-NMR (C.sub.6D.sub.6): 16.7 (NAr CH.sub.3), 19.0 (NAr CH.sub.3), 20.6 (CH.sub.3 Me.sub.2Pyr), 21.2 (CH.sub.3 Me.sub.2Pyr) 30.2 (CH.sub.3 neophylidene), 34.7 (CH.sub.3 neophylidene), 55.1 (C neophylidene), 107.7 (CH Me.sub.2Pyr), 110.8 (CH Me.sub.2Pyr), 123.8 (C3-phen), 124.5 (C3-phen), 124.9 (NAr C.sub.para), 125.5 (C5-phen), 126.0 (neophylidene Ph C.sub.para), 127.0 (NAr C.sub.meta), 126.9 (neophylidene Ph C.sub.ortho), 126.8 (C5-phen), 128.3 (neophylidene Ph C.sub.meta), 128.7 (C4a-phen, NAr C.sub.meta), 129.2 (C4a-phen), 133.7 (NAr C.sub.ortho), 137.6 (C4-phen), 138.4 (C4-phen), 140.4 (NAr C.sub.ortho), 145.0 (C1a-phen), 147.2 (C1a-phen), 153.5 (neophylidene Ph C.sub.ipso), 154.4 (NAr C.sub.ipso), 155.3 (C2-phen), 160.1 (C2-phen), 287.4 ppm (W=CH).

Example 5

[0055] A glass reactor equipped with a stirrer was charged with 0.072 g (1/500 mol/mol) of (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy)2,6-dimethylphenylimidotungsten(VI) (2,5-dimethylpyrrolido)(neophylidene)(1,10-phenanthroline) obtained in Example 1, and 1 g of toluene. After the addition of 5.0 g of dicyclopentadiene, 20.0 g of cyclohexane, 0.21 g of 1-hexene, and a solution prepared by dissolving 0.0105 g of anhydrous zinc chloride in 5 g of 1,4-dioxane, a polymerization reaction was performed at 50 C. White turbidity due to 1,10-phenanthroline-zinc was observed immediately after the initiation of the polymerization reaction. After 3 hours had elapsed, a large quantity of acetone was poured into the reaction mixture to aggregate the precipitate, and the aggregate was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The yield of the resulting ring-opening polymer was 4.3 g, and the ring-opening polymer had a number average molecular weight of 14,000 and a cis content of 97%.

[0056] A glass reactor equipped with a stirrer was charged with 2.5 g of the resulting dicyclopentadiene ring-opening polymer and 21 g of p-toluenesulfonylhydrazide. After the addition of 500 ml of p-xylene, a hydrogenation reaction was performed at 125 C. for 5 hours. The reaction mixture was poured into a large quantity of methanol to completely precipitate the resulting hydrogenated dicyclopentadiene ring-opening polymer, which was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The hydrogenation ratio of the resulting hydrogenated ring-opening polymer was 99% or more, and the ratio of racemo diads in the hydrogenated ring-opening polymer was 92% and syndiotactic. DSC analysis of the obtained hydrogenated ring-opening polymer showed a melting point, suggesting its crystalline nature.

Example 6

[0057] A glass reactor equipped with a stirrer was charged with 0.076 g (1/500 mol/mol) of (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy)2,6-diisopropylphenylimidotungsten(VI) (2,5-dimethylpyrrolido)(neophylidene)(1,10-phenanthroline) obtained in Example 2, and 1 g of toluene. After the addition of 5.0 g of dicyclopentadiene, 20.0 g of cyclohexane, 0.21 g of 1-hexene, and a solution prepared by dissolving 0.0105 g of anhydrous zinc chloride in 5 g of 1,4-dioxane, a polymerization reaction was performed at 50 C. White turbidity due to 1,10-phenanthroline-zinc was observed immediately after the initiation of the polymerization reaction. After 3 hours had elapsed, a large quantity of acetone was poured into the reaction mixture to aggregate the precipitate, and the aggregate was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The yield of the resulting ring-opening polymer was 4.4 g, and the ring-opening polymer had a number average molecular weight of 10,900 and a cis content of 81%.

[0058] A glass reactor equipped with a stirrer was charged with 2.5 g of the resulting dicyclopentadiene ring-opening polymer and 21 g of p-toluenesulfonylhydrazide. After the addition of 500 ml of p-xylene, a hydrogenation reaction was performed at 125 C. for 5 hours. The reaction mixture was poured into a large quantity of methanol to completely precipitate the resulting hydrogenated dicyclopentadiene ring-opening polymer, which was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The hydrogenation ratio of the resulting hydrogenated ring-opening polymer was 99% or more, and the ratio of racemo diads in the hydrogenated ring-opening polymer was 78% and syndiotactic. DSC analysis of the obtained hydrogenated ring-opening polymer showed a melting point, suggesting its crystalline nature.

Example 7

[0059] A glass reactor equipped with a stirrer was charged with 0.072 g (1/500 mol/mol) of (nonafluoro-tert-butyl alkoxy)2,6-dimethylphenylimidotungsten(VI) (2,5-dimethylpyrrolido)(neophylidene)(1,10-phenanthroline) obtained in Example 3, and 1 g of toluene. After the addition of 5.0 g of dicyclopentadiene, 20.0 g of cyclohexane, 0.21 g of 1-hexene, followed by a solution of 0.0105 g of anhydrous zinc chloride in 5 g of 1,4-dioxane, a polymerization reaction was performed at 50 C. White turbidity due to the presence of 1,10-phenanthroline-zinc was observed immediately after the initiation of the polymerization reaction. After 1 hour had elapsed, a large quantity of acetone was poured into the reaction mixture to aggregate the precipitate, and the aggregate was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The yield of the resulting ring-opening polymer was 4.7 g, and the ring-opening polymer had a number average molecular weight of 5,500 and a cis content of 94%.

[0060] A glass reactor equipped with a stirrer was charged with 2.5 g of the resulting dicyclopentadiene ring-opening polymer and 21 g of p-toluenesulfonylhydrazide. After the addition of 500 ml of p-xylene, a hydrogenation reaction was performed at 125 C. for 5 hours. The reaction mixture was poured into a large quantity of methanol to completely precipitate the resulting hydrogenated dicyclopentadiene ring-opening polymer, which was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure.

[0061] The hydrogenation ratio of the resulting hydrogenated ring-opening polymer was in excess of 99% and the ratio of racemo diads in the hydrogenated ring-opening polymer was 93% and syndiotactic. DSC analysis of the obtained hydrogenated ring-opening polymer showed a melting point, suggesting its crystalline nature.

Example 8

[0062] A glass reactor equipped with a stirrer was charged with 0.072 g (1/500 mol/mol) of Mo(CHCMe.sub.2Ph)(NAr.sup.diiPr)(OCMe(CF.sub.3).sub.2).sub.2(1,10-phenantroline), obtained as described in Angew. Chem. Int. Ed. 2011, 50, 8829-7832, and 1 g of toluene. After the addition of 5.0 g of dicyclopentadiene, 20.0 g of cyclohexane, 0.21 g of 1-hexene, followed by a solution of 0.0105 g of anhydrous zinc chloride in 5 g of 1,4-dioxane, a polymerization reaction was performed at 50 C. White turbidity due to the presence of 1,10-phenanthroline-zinc was observed immediately after the initiation of the polymerization reaction. After 1 hour had elapsed, a large quantity of acetone was poured into the reaction mixture to aggregate the precipitate, and the aggregate was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure. The yield of the resulting ring-opening polymer was 4.6 g, and the ring-opening polymer had a number average molecular weight of 3,800 and a cis content of 66%.

[0063] A glass reactor equipped with a stirrer was charged with 2.5 g of the resulting dicyclopentadiene ring-opening polymer and 21 g of p-toluenesulfonylhydrazide. After the addition of 500 ml of p-xylene, a hydrogenation reaction was performed at 125 C. for 5 hours. The reaction mixture was poured into a large quantity of methanol to completely precipitate the resulting hydrogenated dicyclopentadiene ring-opening polymer, which was filtered off, washed, and dried at 40 C. for 24 hours under reduced pressure.

[0064] The hydrogenation ratio of the resulting hydrogenated ring-opening polymer was 99% or more, and the ratio of racemo diads in the hydrogenated ring-opening polymer was 39% and not syndiotactic (iso-biased). DSC analysis of the obtained hydrogenated ring-opening polymer showed no melting point, suggesting its amorphous nature.