Siloxane-functionalized platinum (iv) precatalysts

Abstract

This invention relates to compounds of Formula 1, wherein Ar, X, R1, R2, R3, R4, R7, x, y, and z are as defined herein. This invention provides a precatalyst that rapidly decomposes into a platinum state that promotes hydrosilylation upon irradiation with light of an appropriate wavelength.

Description

Background Technology

[0001] This invention relates to photoactivated siloxane-functionalized platinum(IV) (Pt(IV)) precatalysts, particularly for hydrosilylation reactions. Hydrosilylation is commonly used in the organosilicon industry for the synthesis of organosilicon polymers and crosslinking materials. UV-initiated hydrosilylation using photoactivated precatalysts is becoming increasingly popular because the energy input required to trigger the reaction is lower compared to thermal activation methods. Pt(IV) materials such as cyclopentadienyltrimethylplatinum and their analogues are known to be used as photoactivated precatalysts for hydrosilylation (see US 4,510,094, US 8,088,878, and US 10,392,479); Pt(IV) decomposes under UV irradiation to form catalytically active Pt(O) materials. However, these known precatalysts typically exhibit undesirable volatility, and reactions using these precatalysts tend to proceed slowly. Pt(IV) materials such as cyclopentadienyltrimethylplatinum and their analogues are known to be used as photoactive precatalysts for hydrosilylation (see US 4,510,094, US 8,088,878 and US 10,392,479); Pt(IV) decomposes under UV irradiation to form catalytically active Pt(0) materials. However, these known precatalysts generally exhibit undesirable volatility, and reactions using these precatalysts tend to proceed slowly. Summary of the Invention

[0002] This invention relates to a compound of Formula 1:

[0003]

[0004] Where Ar is phenyl, naphthyl, or anthracene; X is C2-C 12 Hydrocarbon diradical; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, each R is a C1-C6-alkyl, C1-C6-alkoxy, Ar, NO2, acetyl, trifluoromethyl, or halogroup; 3 Independently C1-C-6-alkyl, C1-C-6-alkoxy, phenyl, or -(OSi(R) 5 )2) w OSi(R 6 )3; Each R 4 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 5 Independently C1-C6-alkyl, phenyl, or OSi(R) 4 )3; Each R 6 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 7Independently, it is H, methyl, ethyl, or phenyl; m is 0 or 1; x is 0 to 5; y is 0 to 4; and the sum of z+w is 0 to 20. This invention addresses a need in the art by providing a Pt(IV) precatalyst that rapidly decomposes into a catalytically active Pt(0) state under light irradiation. Detailed Implementation

[0005] This invention relates to a compound of Formula 1:

[0006]

[0007] Where Ar is phenyl, naphthyl, or anthracene; X is C2-C 12 Hydrocarbon diradical; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, each R is a C1-C6-alkyl, C1-C6-alkoxy, Ar, NO2, acetyl, trifluoromethyl, or halogroup; 3 Independently C1-C-6-alkyl, C1-C-6-alkoxy, phenyl, or -(OSi(R) 5 )2) w OSi(R 6 )3; Each R 4 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 5 Independently C1-C6-alkyl, phenyl, or OSi(R) 4 )3; Each R 6 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 7 Independently, it is H, methyl, ethyl, or phenyl; m is 0 or 1; x is 0 to 5; y is 0 to 4; and the sum of z + w is 0 to 20. Preferably, z is 1 to 20. Preferably, when z is 1 to 20, each R 4 For methyl, and when z is 0, each R 4 For phenyl; each R 5 Independently methyl, phenyl, or -OSi(OCH3)3; and each R 7 For H.

[0008] The compounds of the present invention are advantageously prepared using the following steps. In the first step, an alkali metal cyclopentadiene, such as sodium cyclopentadiene (Na-Cp), is reacted with R... 1 -Br contact to form alkyl or phenyl-substituted cyclopentadiene (R 1 ) x -Cp. Appropriate R 1 Examples of groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Then make (R... 1 )x -Cp reacts with alkali metal bis(trimethylsilyl)amides such as potassium or sodium bis(trimethylsilyl)amino with alkyl lithium such as n-butyllithium to form (R 1 ) x -Cp alkali metal salts (intermediate A):

[0009]

[0010] Then Li-(R) can be made 1 )-Cp and another equivalent R 1 -Br contact to form further substituted cyclopentadiene, and the reaction can be repeated until (R) is obtained. 1 5-substituted Cp-alkali metals.

[0011] In a separate series of steps, a dibromomethylaryl compound, such as dibromomethylbenzene, is contacted with an alkenyl-functionalized Grignard reagent to form an alkenyl-functionalized bromomethylaryl compound, preferably an alkenyl-functionalized bromomethylbenzene (intermediate B):

[0012]

[0013] Where n ranges from 0 to 9. Intermediate B can be used as a precursor to prepare the intermediate of compound of formula 1, where X is C3-C. 12 Hydrocarbon diradical. A similar intermediate can be prepared by using commercially available bromomethylstyrene as intermediate B, where X is a C2 hydrocarbon diradical.

[0014] In a separate series of steps, a toluene-functionalized Grignard reagent, such as (p-toluene)magnesium bromide, is contacted with a halide-functionalized dimethyl(vinyl)silyl compound, such as dimethyl(vinyl)chlorosilane, to form a toluene-functionalized dimethyl(vinyl)silyl compound:

[0015]

[0016] Then, in the presence of a free radical initiator such as azobisisobutyronitrile (AIBN), the tolyl-functionalized dimethyl (vinyl)silyl compound can be treated with a brominating agent such as N-bromosuccinimide (NBS) to generate dimethyl (vinyl)silyl-functionalized bromomethylbenzene (intermediate B'), wherein each R 7 Let H be the number of elements, and m be 1:

[0017]

[0018] In the presence of a platinum catalyst, intermediate B or B' advantageously contacts a siloxane containing Si-H functional groups to form intermediate C:

[0019]

[0020] Norbornene diene dimethylplatinum(II) ((NBD)PtMe2) was dissolved in a suitable donor solvent such as pyridine, and then contacted with intermediate C under conditions sufficient to form an oxidative addition product, followed by contact with intermediate A in the same reaction vessel to form a compound of formula 1:

[0021]

[0022] Ar is preferably phenyl; y is preferably 0, 1, 2 or 3; each R 3 Preferably, it is phenyl, methyl, or -(OSi(R) 5 )2) w OSi(R 6 )3. R 5 Preferably methyl, phenyl, or -OSi(OCH3)3; each R 6 Preferably methyl; each R 7 Preferably, it is H; and the sum of z + w is preferably 1 to 15. On the other hand, w is 0; on the other hand, z is 1 to 15.

[0023] Specific examples of the compounds of the present invention include the following:

[0024]

[0025] In another aspect, the present invention is a method comprising the steps of: contacting a solution of norbornene diene dimethylplatinum(II) and an N-donor solvent such as pyridine or quinoline with intermediate C under conditions suitable for forming an oxidative addition intermediate; and then contacting the oxidative addition intermediate with intermediate A under conditions suitable for forming a compound of formula 1. Suitable pyridines include pyridine, 4-methylpyridine, 4-tert-butyl-butylpyridine, 4-methoxypyridine, and 4-dimethylaminopyridine. Suitable quinolines include quinoline, 8-methylquinoline, and 8-methoxyquinoline.

[0026] The compounds of this invention are Pt(IV) precatalysts that exhibit excellent efficiency in promoting UV-triggered hydrosilylation chemistry. This efficiency is believed to stem from two aspects: firstly, Pt-(R... 7 The presence of the 2Ar fragment provides a mechanism for the precatalyst to undergo homolytic cleavage and simultaneously transform into the catalytically active Pt(0) state; secondly, the presence of siloxane functional groups promotes improved dispersion of the precatalyst in siloxane media. The relatively low vapor pressure of the precatalyst is also beneficial, as the amount of precatalyst required to initiate hydrosilylation is lower due to its reduced volatility.

[0027] Example

[0028] Intermediate Example 1 - Preparation of (NBD)PtMe2

[0029] (NBD)PtMe2 was prepared using a modified procedure according to Eur. J. Inorg. Chem. 2015, 226–239, in which deionized water was used instead of concentrated HCl to quench the reaction. The NMR spectra of the resulting product matched those previously reported.

[0030] Intermediate Example 2 - Preparation of 1-(bromomethyl)-4-(but-3-en-1-yl)benzene

[0031] In a nitrogen-filled glove box, 1,4-bis(bromomethyl)benzene (8.00 g, 30.31 mmol, 1 equivalent) was placed in a 250-mL wide-mouth glass flask along with diethyl ether (50 mL), THF (20 mL), and a magnetic stir bar. The resulting colorless suspension was stored at -25°C for 1 hour, and then a 1.0 M solution of allyl magnesium bromide in diethyl ether (28.8 mL, 28.8 mmol, 0.95 equivalent) was added dropwise. The resulting gray suspension was warmed to ambient temperature and stirred vigorously for 72 hours. The reaction mixture was then removed from the glove box and diluted with deionized water (25 mL) to homogenize the heterogeneous mixture. The resulting biphasic mixture was transferred to a separatory funnel, and the organic layer was washed with water (2 x 10 mL) and brine (2 x 10 mL). The organic layer was collected, dried over MgSO4, filtered, and concentrated by rotary evaporation to a nearly colorless oil. The crude material was purified by rapid chromatography using 100% hexane as the solvent. The desired product was collected in fractions 7-24. 1 Purity was confirmed by 1H NMR and GC-MS. Yield: 2.6 g, 38.1%. 1 H NMR (400MHz, CDCl3) δ 7.35 – 7.26 (m, 2H), 7.17 (d, J =7.9Hz, 2H), 5.85 (ddt, J = 16.9, 10.2, 6.6Hz, 1H), 5.10 – 4.95 (m, 2H), 4.50(s, 2H), 2.71 (dd, J = 9.0, 6.7Hz, 2H), 2.37 (qd, J = 7.2, 1.6Hz, 2H). 13C NMR(101MHz, CDCl3) δ 142.47, 138.37, 137.97, 135.41, 129.17, 129.02, 128.47,115.24, 114.94, 77.48, 77.36, 77.16, 76.84, 35.69, 35.41, 35.20, 35.11,33.82.

[0032] Intermediate Example 3 - 1-(4-(4-(bromomethyl)phenyl)butyl)-1,1,3,3,3-pentamethyldisiloxane Preparation of (Br-benzyl-MM)

[0033] 1-(bromomethyl)-4-(but-3-en-1-yl)benzene (1.00 g, 4.44 mmol, 1 equivalent) was added to a 60-mL glass vial equipped with a diaphragm cap and a magnetic stir bar. Karstedt catalyst (3 drops of xylene solution of 2% Pt by weight) was added, and the mixture was heated to 50 °C, followed by the dropwise addition of 1,1,1,3,3-pentamethyldisiloxane (MM') (0.87 mL, 4.44 mmol, 1 equivalent). Stirring was continued at 50 °C for 24 hours. The mixture was cooled to room temperature, diluted with hexane (4 mL), and stirred with activated carbon for 5 to 10 minutes. The mixture was then passed through a 0.45-μm PTFE syringe filter, and volatiles were removed by rotary evaporation to give an almost colorless liquid. Yield: 1.62 g, 97.7%. 1 H NMR (500MHz, CDCl3) δ 7.32 (d,J = 8.1Hz, 2H), 7.17 (d, J = 8.1Hz, 2H), 4.52 (s, 2H), 2.65 – 2.57 (m, 2H),1.73 – 1.57 (m, 2H), 1.50 – 1.29 (m, 2H), 0.66 – 0.46 (m, 2H), 0.08 (s, 9H), 0.06 (s, 6H). 13 C NMR (126MHz, CDCl3) δ 143.55, 135.13, 129.12, 128.99, 35.57, 35.14, 33.93, 23.14, 18.35, 2.12, 0.52.

[0034] Intermediate Example 4 - 1-(4-(4-(bromomethyl)phenyl)butyl)-polydimethylsiloxane (Br-benzyl- Preparation of PDMS :

[0035] 1-(bromomethyl)-4-(but-3-en-1-yl)benzene (0.680 g, 3.02 mmol, 1 equivalent) was added to a 60-mL glass vial equipped with a diaphragm cap and a magnetic stir bar. Karstedt catalyst (3 drops of xylene solution containing 2% Pt by weight) was added, and the mixture was heated to 50 °C. Then, monohydride-terminated polydimethylsiloxane material (dp=10⁻¹², Gelest, product code MCR-H07) (3.04 g, 3.02 mmol, 1 equivalent) was added dropwise. After 2 hours, the mixture was cooled to ambient temperature, diluted with hexane (4 mL), and stirred with activated carbon for 5 to 10 minutes. The mixture was then filtered through a 0.45 μm syringe, and volatiles were removed under vacuum to obtain a pale yellow liquid. 1 ¹H NMR characterization confirmed the identity of the target product. Yield: 3.47 g, 93.3%. 1 ¹H NMR (400MHz, C6D6) δ 7.05 (d, J = 8.0Hz, 2H), 6.95 (d, J = 7.8Hz, 2H), 4.05 (s, 2H), 2.47 (t, J = 7.7Hz, 2H), 1.58 (p, J = 7.4Hz, 2H), 1.47 – 1.33 (overlapping resonance, 6H), 0.99 – 0.92 (overlapping resonance, 4H), 0.68 – 0.56 (overlapping resonance, 4H), 0.30 – 0.15 (overlapping resonance, 85H). 13 C NMR (101MHz, C6D6) δ 143.20, 135.64,129.37, 128.99, 35.73, 35.43, 33.54, 26.82, 25.93, 23.34, 18.47, 18.39,14.09, 1.51, 1.44, 1.42, 0.45.

[0036] Intermediate Example 5 - 3-(4-(4-(bromomethyl)phenyl)butyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane Preparation of alkane (Br-benzyl-MDM)

[0037] 1-(bromomethyl)-4-(but-3-en-1-yl)benzene (0.180 g, 0.80 mmol, 1 equivalent) was added to a 60-mL glass vial fitted with a diaphragm cap and a magnetic stir bar. Karstedt catalyst (2 drops of xylene solution of 2% Pt by weight) was added, and the mixture was heated to 50 °C, followed by the dropwise addition of 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD'M) (0.217 mL, 0.80 mmol, 1 equivalent). After 2 hours, the mixture was cooled to ambient temperature, and the reaction mixture was diluted with hexane (4 mL) and stirred with activated carbon for 5 to 10 minutes. The mixture was then passed through a 0.45 μm PTFE syringe filter, and volatiles were removed by rotary evaporation to give an almost colorless liquid. Yield: 0.338 g, 94.4%. 1 H NMR (500MHz,C6D6) δ 7.03 (d, J = 8.0Hz, 2H), 6.93 (d, J = 8.4Hz, 2H), 4.05 (s, 2H), 2.45(t, J = 7.6Hz, 2H), 1.57 (p, J = 7.5Hz, 2H), 1.49 – 1.35 (m, 2H), 0.68 – 0.48 (m, 2H), 0.16 (s, 18H), 0.13 (s, 3H). 13 C NMR (126MHz, C6D6) δ 143.15, 135.61, 129.35, 129.01, 35.70, 35.16, 33.56, 23.17, 17.96, 2.04, 0.06.

[0038] Intermediate Example 6: Preparation of dimethyl(p-tolyl)(vinyl)silane

[0039] Dichloromethyl(vinyl)silane (2.00 g, 16.58 mmol, 1 equivalent) was placed in a 100-mL wide-mouth glass flask with THF (30 mL) and a magnetic stir bar. The colorless solution was stored at -25°C for 1 hour. Once cooled, a 1.0 M solution of p-tolyl magnesium bromide in THF (16.58 mL, 16.58 mmol, 1 equivalent) was slowly added. The reaction mixture was then slowly warmed to ambient temperature and stirred for 48 hours. A portion (8 mL) of 1,4-dioxolane was then added, producing a colorless solid precipitate. The suspension was then passed through a diatomaceous earth pad at the top of a disposable PTFE glass filter and volatiles were removed under vacuum to give a pale yellow liquid. Yield: 1.83 g, 62.6%. 1H NMR (400MHz, C6D6) δ 7.49 – 7.42 (m, 2H), 7.11– 7.04 (m, 2H), 6.30 (dd, J = 20.3, 14.6Hz, 1H), 5.99 (dd, J = 14.6, 3.8Hz,1H), 5.74 (dd, J = 20.3, 3.8Hz, 1H), 2.14 (s, 3H), 0.31 (s, 6H). 13 C NMR (101MHz, C6D6) δ 138.95, 138.59, 134.36, 132.76, 129.01, 120.18, 21.47, -2.63.

[0040] Intermediate Example 7 - Preparation of (4-(bromomethyl)phenyl)dimethyl(vinyl)silane

[0041] Dimethyl(p-tolyl)(vinyl)silane (1.10 g, 6.24 mmol, 1 equivalent) was placed in a 40-mL glass vial with previously dried deoxyethyl acetate (25 mL) on a molecular sieve, N-bromosuccinimide (1.11 g, 6.24 mmol, 1 equivalent), azobisisobutyronitrile (0.205 g, 1.25 mmol, 1 equivalent), and a magnetic stir bar. The reaction mixture was then heated at 70 °C for a total of 18 hours, followed by cooling to ambient temperature. The mixture was then concentrated under vacuum onto silica gel and purified by ISCO chromatography using 100% hexane as the solvent. The desired product was separated from fractions 5-11. Yield: 0.360 g, 22.6%. 1 H NMR (400MHz, C6D6) δ 7.35 (d, J = 8.0Hz, 2H), 7.09 (d, J =8.0Hz, 2H), 6.21 (dd, J = 20.2, 14.6Hz, 1H), 5.96 (dd, J = 14.6, 3.7Hz, 1H), 5.67 (dd, J = 20.2, 3.7Hz, 1H), 4.00 (s, 2H), 0.24 (s, 6H). 13 C NMR (101MHz, C6D6) δ 138.96, 138.78, 137.88, 134.56, 133.16, 128.69, 128.67, 33.35, -2.88.

[0042] Intermediate Example 8 - 3-(2-((4-(bromomethyl)phenyl)dimethylsilyl)ethyl)-1,1,1,3,5, Preparation of 5,5-heptamethyltrisiloxane (Br-benzyl-SiMe2-MDM)

[0043] (4-(bromomethyl)phenyl)dimethyl(vinyl)silane (0.105 g, 0.41 mmol, 1 equivalent) was added to a 30-mL glass vial fitted with a diaphragm cap, a magnetic stir bar, and toluene (2 mL). Karstedt catalyst (1 drop of xylene solution of 2 wt% Pt) was added, and the mixture was heated to 50 °C, followed by the dropwise addition of 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD'M) (0.112 mL, 0.41 mmol, 1 equivalent). After 2 hours, the mixture was cooled to ambient temperature, and the reaction mixture was diluted with hexane (4 mL) and stirred with activated carbon for 5 minutes. The mixture was then passed through a 0.45 μm PTFE syringe filter, and volatiles were removed by rotary evaporation to give an almost colorless liquid. Yield: 0.183 g, 93.1%. 1 H NMR(400MHz, C6D6) δ 7.43 – 7.34 (m, 2H), 7.12 – 7.07 (m, 2H), 4.00 (s, 2H), 0.88– 0.78 (m, 2H), 0.58 – 0.50 (m, 2H), 0.22 (s, 6H), 0.16 (s, 18H), 0.14 (s, 3H). 13 C NMR (101MHz, C6D6) δ 139.73, 138.77, 134.31, 128.69, 33.36, 10.13,7.49, 2.06, -0.77, -3.53.

[0044] Example 1 - Preparation of CpPtMe2-Benzyl-MM

[0045]

[0046] In a nitrogen-filled glove box, (NBD)PtMe2 (0.20 g, 0.63 mmol, 1 equivalent) was placed in a 20-mL glass vial with pyridine (5 mL) and a magnetic stir bar. The resulting golden solution was stirred at ambient temperature for 5 minutes, and then Br-benzyl-MM (intermediate 3, 0.235 g, 0.63 mmol, 1 equivalent) was added dropwise. After stirring for another 4 hours, NaCp (0.067 g, 0.76, 1.2 equivalent) was added directly to the reaction mixture as a solid at ambient temperature. The reaction mixture was stirred at ambient temperature for 18 hours. Volatiles were removed under vacuum, and the residue was extracted into DCM (3 x 5 mL) by grinding with dichloromethane (DCM, 2 x 4 mL) and filtered through a diatomaceous earth pad, followed by washing with additional DCM (10 mL). The combined extracts were concentrated under vacuum to give a red / maroon oil. The material was then removed from the glove box and extracted again into DCM (10 mL), filtered through a Florisil pad, and washed with another 10 to 15 mL of DCM. The filtrate was concentrated into a red oil by rotary evaporation. This oil was dissolved in hexane (5 mL), filtered through a Florisil pad, and the filtrate was concentrated into an almost colorless oil. Yield: 0.272 g, 73.9%. 1 H NMR (500MHz, C6D6) δ 7.21 – 7.17 (m, 2H), 7.06– 7.02 (m, 2H), 5.13 – 4.84 (m, 5H), 3.14 (m, 2 J Pt-H = 97.2Hz, 2H), 2.57 (t, J= 7.7Hz, 2H), 1.80 – 1.60 (m, 2H), 1.52 – 1.39 (m, 2H), 1.22 (m, 2 J Pt-H =82.6Hz, 6H), 0.73 – 0.46 (m, 2H), 0.14 (s, 9H), 0.12 (s, 6H). 13 C NMR (126MHz, C6D6) δ 149.13, 138.85, 128.58, 128.44, 97.62, 35.80, 35.65, 23.40, 18.61,11.52 (m, 1 J Pt-C = 664.6Hz), 2.17, 0.59, -17.98 (m, 1 J Pt-C = 738.1Hz). 195Pt NMR (85MHz, C6D6) δ -4968.89.

[0047] Example 2 - Preparation of (CH-3)5-CpPtMe2-(benzyl-MM)

[0048]

[0049] In a nitrogen-filled glove box, (NBD)PtMe2 (0.130 g, 0.41 mmol, 1 equivalent) was placed in a 20-mL glass vial along with pyridine (3 mL) and a magnetic stir bar. The resulting golden solution was stirred at ambient temperature for 10 minutes, and then Br-benzyl-MM (0.153 g, 0.41 mmol, 1 equivalent) was added dropwise to the solution. After stirring for another 3 hours, Li(CH3)5Cp (0.070 g, 0.49 g, 1.2 equivalent) was added directly to the reaction mixture as a solid at ambient temperature. Additional pyridine (2 mL) was added to facilitate quantitative transfer of all Cp salts to the reaction vial. The reaction mixture was stirred at ambient temperature for another 2 hours, and then passed through a diatomaceous earth pad on top of a Florisil pad contained in a 0.45-μm PTFE syringe filter. The pad and filter were rinsed with hexane (4 x 3 mL) and combined with the filtrate. The volatiles were then removed under vacuum, and the residue was ground with hexane (2 x 4 mL), then extracted into hexane (5 x 5 mL), and filtered again through a new Florisil pad and a 0.45-μm PTFE syringe. The extract was then concentrated under vacuum to give a pale yellow oil. The material was stored at -25°C for 18 hours, after which it was extracted for the last time into hexane (3 mL), and then filtered through a new Florisil pad. The pad was washed with an additional hexane, and the filtrate was concentrated under vacuum to an almost colorless oil. Yield: 0.180 g, 67.2%. 1 H NMR (400MHz, C6D6)δ 7.21 – 7.15 (m, 2H), 7.12 – 7.00 (m, 2H), 2.96 (m, 2 J Pt-H = 99.6Hz, 2H), 2.65– 2.48 (m, 2H), 1.74 – 1.62 (m, 2H), 1.49 – 1.39 (m, 2H), 1.35 (m, 3 J Pt-H =6.4Hz, 15H), 0.82 (m, 2 J Pt-H = 78.9Hz, 6H), 0.67 – 0.55 (m, 2H), 0.15 (s, 9H), 0.13 (s, 6H). 13C NMR (126MHz, C6D6) δ 145.89, 138.07, 128.35, 102.66, 35.86,35.76, 23.30, 18.68, 12.33 (m, 1 J Pt-C = 334.9Hz), 7.47, 2.16, 0.61, -6.55 (m, 1 J Pt-C = 371.5Hz). 195 Pt NMR (85MHz, C6D6) δ -5036.4.

[0050] Example 3 - Preparation of CH3-CpPtMe2-(Benzyl-PDMS)

[0051]

[0052] In a nitrogen-filled glove box, (NBD)PtMe2 (0.148 g, 0.47 mmol, 1 equivalent) was placed in a 20-mL glass vial along with pyridine (3 mL) and a magnetic stir bar. The resulting golden solution was stirred at ambient temperature for 10 minutes, and then Br-benzyl-PDMS (dp = 10⁻¹², 0.574 g, 0.47 mmol, 1 equivalent) was added dropwise to the solution. Additional pyridine (1 mL) was added to ensure quantitative transfer of the siloxane reagent to the reaction vial. After stirring for another 3 hours, Li₂ was added at ambient temperature. Me Cp (0.048 g, 0.56, 1.2 equivalents) was added directly to the reaction mixture in solid form. The reaction mixture was stirred at ambient temperature for another 2 hours, then passed through a diatomaceous earth pad on top of a Fluorisil pad and filtered through a 0.45-μm PTFE syringe filter. The pad and filter were washed with hexane (4 x 3 mL) and combined with the filtrate. The volatiles were then removed under vacuum, and the residue was milled with hexane (3 x 3 mL), extracted into hexane (3 x 5 mL), and filtered through a new Fluorisil pad and a 0.45-μm PTFE syringe. The extract was then concentrated under vacuum to give a pale yellow oil. The material was stored at -25°C for 18 hours, then extracted for the last time into hexane (3 mL) and filtered through a new Fluorisil pad, washing with another 5 to 7 mL of hexane. The filtrate was then concentrated under vacuum to a nearly colorless oil. Yield: 0.420 g, 61.9%. 1H NMR (400MHz, C6D6) δ 7.21 (d, J = 7.9Hz, 2H), 7.05 (d, J =7.9Hz, 2H), 4.98 (t, J = 2.3Hz, 2H), 4.70 (t, J = 2.4Hz, 2H), 3.17 (m, 2 J Pt-H =97.5Hz, 2H), 2.69 – 2.49 (m, 2H), 1.70 (p, J = 7.5Hz, 2H), 1.51 – 1.32 (m,3H), 1.16 (m, 2 J Pt-H = 81.7Hz, 6H), 0.99 – 0.89 overlapping multiple peaks, 4H), 0.73 – 0.57 (m,4H), 0.32 – 0.15 (m, 85H). 13 C NMR (101MHz, C6D6) δ 149.16, 138.66, 114.48,98.58, 93.56, 35.83, 35.73, 26.82, 25.94, 23.39, 18.55, 18.39, 14.09, 11.49,11.26 (m, 1 J Pt-C = 663.3 Hz), 1.54, 1.51, 1.45, 1.43, 0.48, 0.46, -14.60 (m, 1 J Pt-C = 740.6Hz). 195 Pt NMR (86MHz, C6D6) δ -4990.79.

[0053] Example 4 - Preparation of CH3-CpPtMe2-(Benzyl-MDM)

[0054]

[0055] In a nitrogen-filled glove box, (NBD)PtMe2 (0.85 g, 0.27 mmol, 1 equivalent) was placed in a 20-mL glass vial along with pyridine (2 mL) and a magnetic stir bar. The resulting golden solution was stirred at ambient temperature for 20 minutes, and then Br-benzyl-MDM (0.120 g, 0.27 mmol, 1 equivalent) in pyridine (0.5 mL) was added dropwise to the solution. After stirring at ambient temperature for 2 hours, solid Li was added at ambient temperature. MeCp (0.028 g, 0.32 mmol, 1.2 equivalences) was added directly to the reaction mixture in solid form. The reaction mixture was stirred at ambient temperature for 2 hours and then filtered through a diatomaceous earth pad on top of a Fluorisil pad and a 0.45-μm PTFE syringe filter. The pad and filter were washed with hexane (2 x 3 mL) and combined with the filtrate. The volatiles were then removed under vacuum, and the residue was milled with hexane (3 x 3 mL), extracted into hexane (3 x 5 mL), and filtered through a new Fluorisil pad and a 0.45-μm PTFE syringe. The extract was then concentrated under vacuum to give a pale yellow oil. The material was stored at -25 °C for 18 hours and then extracted for the last time into hexane (3 mL) and filtered through a new Fluorisil pad, washing it with another 5 to 7 mL of hexane. The filtrate was concentrated under vacuum to a nearly colorless oil. Yield: 0.101 g, 56.1%. 1 H NMR (400MHz, C6D6) δ 7.20 (d, J = 8.0Hz, 2H), 7.04 (d, J= 8.1Hz, 2H), 4.98 (t, J = 2.2Hz, 2H), 4.69 (t, J = 2.3Hz, 2H), 3.17 (m, 2 J Pt-H = 97.5Hz, 2H), 2.58 (dd, J = 9.5, 5.7 Hz, 2H), 1.70 (p, J = 7.4Hz, 2H), 1.55(s, 3H), 1.54 – 1.44 (m, 2H), 1.16 (m, 2 J Pt-H = 81.7Hz, 2H), 0.72 – 0.56 (m,2H), 0.18 (s, 18H), 0.14 (s, 3H). 13 C NMR (101MHz, C6D6) δ 149.11 (m, 2 J Pt-C =58.3Hz), 138.63, 114.48, 98.58, 93.55, 35.84, 35.51, 23.30, 18.03, 11.49,11.26 (m, 1 J Pt-C = 663.2Hz), 2.08, 0.08, -14.59 (m, 1 J Pt-C = 740.6Hz). 195Pt NMR(86MHz, C6D6) δ -4991.45.

[0056] Example 5 - Preparation of CH3-CpPtMe2-(Benzyl-SiMe2-MDM)

[0057]

[0058] (NBD)PtMe2 (0.082 g, 0.26 mmol, 1 equivalent) was placed in a 30-mL glass vial along with pyridine (2 mL) and a magnetic stir bar. The resulting pale yellow solution was stirred at ambient temperature for 20 minutes, and then Br-benzyl-SiMe2-MDM (0.123 g, 0.26 mmol, 1 equivalent) was added dropwise. Additional pyridine (1 mL) was added to ensure quantitative transfer of the bromomethyl reagent to the reaction vial. After a total of 2 hours of stirring, Li was added at ambient temperature. Me Cp (0.027 g, 0.31 mmol, 1.2 equivalences) was added directly to the reaction mixture in solid form. The reaction mixture was stirred at ambient temperature for 1 hour, and then volatiles were removed under vacuum. Hexane was added to the residue to give a suspension, which was then stirred at ambient temperature for 1 hour. The suspension was then passed through a Florisil pad and a 0.45-μm PTFE syringe filter. The filter pad was rinsed with hexane (2 x 5 mL) and combined with the filtrate. The combined filtrate was then concentrated under vacuum to give a yellow liquid, which was extracted again into hexane (6 mL) and filtered one last time through a Florisil pad and a 0.20-μm PTFE syringe filter to give a pale yellow solution. The solution was then concentrated to a pale yellow liquid. Yield: 0.091 g, 50.2%. 1 H NMR (400MHz, C6D6) δ 7.51 – 7.41 (m, 2H), 7.31 – 7.20 (m, 2H), 4.94 (t, J = 2.2Hz, 2H), 4.66 (t, J = 2.3Hz, 2H), 3.15(m, 2 J Pt-H = 99.1Hz, 2H), 1.52 (d, J Pt-H = 6.3Hz, 3H), 1.15 (m, 2 J Pt-H = 81.6Hz, 6H), 0.93 – 0.86 (m, 2H), 0.66 – 0.58 (m, 2H), 0.31 (s, 6H), 0.17 (s, 18H), 0.16 (s, 3H). 13C NMR (101MHz, C6D6) δ 152.81 (d, J = 58.6Hz), 134.19 (J Pt-C =15.4Hz), 133.81 (J Pt-C = 13.9Hz), 114.47 (J Pt-C = 14.3Hz), 98.58, 93.46, 11.41,11.31 (m, 1 J Pt-C = 662.2Hz), 10.32, 7.87, 2.10, -0.75, -3.25 (J Pt-C = 51.3Hz), -14.50 (m, 1 J Pt-C = 736.2Hz). 195 Pt NMR (85MHz, C6D6) δ -5003.26.

[0059] The compounds (precatalysts) of Examples 1-5 were respectively reacted with methyltrimethoxysilane (XIAMETER) ™ OFS-6070 silane (MTM) combination. Each pre-catalyst + MTM mixture is added to vinyl-terminated polydimethylsiloxane (XIAMETER). ™ RBL-9119 polymer (polymer 1) and trimethylsilyl-terminated methylhydrosiloxane-dimethylsiloxane copolymer (DOWSIL) ™ In a premixed blend of polymer 6-3570 (polymer 2), each composition was mixed at 2000 rpm for 30 seconds. (XIAMETER and DOWSIL are trademarks of The Dow Chemical Company or its affiliates.) Table 1 shows the formulations. Formulation 1 uses the compound of Example 1; Formulation 2 uses the compound of Example 2, etc. The amount of precatalyst + solvent was adjusted to achieve an elemental Pt concentration of 18 ppm for each formulation. The precatalyst concentration in MTM refers to the precatalyst concentration as a percentage by weight.

[0060] Table 1 - Polyorganosiloxane Formulations

[0061]

[0062] Gelation point determination

[0063] The gel point time of each sample was measured using the following UV-rheological test: UV-activated hydrogen silanization curing was tested using an MCR-302 rheometer equipped with a UV irradiation accessory. Broadband UV irradiation with wavelengths between 250 nm and 450 nm was applied at a rate of 4 J / cm². 2 UV dose (100mW / cm) 2 (x 40 seconds). The sample thickness was initially set to 0.3 mm. To generate the curing profile, viscoelasticity was monitored by applying oscillatory shear at 10 rad / sec within the linear viscoelastic region. The gelation time was then determined by the G'-G” alternation point. Table 2 shows the gelation time for each formulation.

[0064] Table 2 - Curing Time of Formulations

[0065]

[0066] Formulations prepared using the embodiments of the present invention exhibit excellent reactivity, as demonstrated by a gel point time of <30 minutes.

Claims

1. A compound of formula 1: Where Ar is phenyl, naphthyl, or anthracene; X is C2-C 12 Hydrocarbon diradical; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, each R is a C1-C6-alkyl, C1-C6-alkoxy, Ar, NO2, acetyl, trifluoromethyl, or halogroup; 3 Independently C1-C-6-alkyl, C1-C-6-alkoxy, phenyl, or -(OSi(R) 5 )2) w OSi(R 6 )3; Each R 4 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 5 Independently C1-C6-alkyl, phenyl, or OSi(R) 4 )3; Each R 6 Independently, it is C1-C6-alkylphenyl or C1-C6-alkoxy; each R 7 Independently, it is H, methyl, ethyl, or phenyl; m is 0 or 1; x is 0 to 5; y is 0 to 4; and the sum of z and w is 0 to 20.

2. The compound according to claim 1, wherein Ar is phenyl; each R 1 Independently C1-C4-alkyl or phenyl; each R 2 For H; each R 3 Independently methyl, phenyl, or -(OSi(R) 5 )2) w OSi(R 6 )3; When z is 1 to 20, each R 4 For methyl, and when z is 0, each R 4 For phenyl; each R 5 Independently methyl, phenyl, or -OSi(OCH3)3; and each R 7 For H.

3. The compound according to claim 2, wherein X is a C2-C4 hydrocarbon diradical; and y is 0, 1, or 2.

4. The compound according to claim 3, wherein w is 0; and each R 3 It can be methyl, phenyl, or Si(OCH3)3 independently.

5. The compound according to any one of claims 1 to 4, wherein each R 3 It is methyl or phenyl; and z is 1 to 15.

6. The compound according to claim 5, wherein the compound is selected from the group consisting of the following: 。 7. The compound according to claim 5, wherein the compound is selected from the group consisting of: 。 8. A method comprising the following steps: a) Contacting a solution of norbornene dimethylplatinum(II) and the N-donor solvent with intermediate C under conditions sufficient to form the oxidative addition product: Then b) contact the oxidative addition product with intermediate A under conditions sufficient to form the product of formula 1: Where Ar is phenyl, naphthyl, or anthracene; X is C2-C 12 Hydrocarbon diradical; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, each R is a C1-C6-alkyl, C1-C6-alkoxy, Ar, NO2, acetyl, trifluoromethyl, or halogroup; 3 Independently C1-C-6-alkyl, C1-C-6-alkoxy, phenyl, or -(OSi(R) 5 )2) w OSi(CH3)3; each R 4 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 5 Independently C1-C6-alkyl, phenyl, or OSi(R) 4 )3; Each R 6 Independently, it is C1-C6-alkyl, phenyl, or C1-C6-alkoxy; each R 7 Independently, it is H, methyl, ethyl, or phenyl; m is 0 or 1; x is 0 to 5; y is 0 to 4; and the sum of z and w is 0 to 20.

9. The method according to claim 8, wherein the N-donor solvent is pyridine, Ar is phenyl, and X is C2-C 12 Hydrocarbon diradical; each R 1 Independently C1-C4-alkyl or phenyl; each R 2 For H; each R 3 Independently methyl, methoxy, phenyl or -(OSi(R) 5 )2) w OSi(CH3)3; when z is 1 to 20, each R 4 For methyl, and when z is 0, each R 4 For phenyl; each R 5 Independently -OSi(OCH3)3, methyl or phenyl; and each R 7 For H.

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