Compositions comprising benzyl or allyl functionalized platinum (IV) precatalysts

Abstract

The present invention is a composition comprising: a) a compound functionalized with at least one Si-H group; b) a compound functionalized with at least one olefin group; and c) a compound of Formula 1: wherein x, R1, R2, and R3 are as defined herein. The composition provides a precatalyst that rapidly decomposes into a platinum state that promotes hydrosilylation upon irradiation with light of an appropriate wavelength. Formula 1

Description

Background Technology

[0001] This invention relates to compositions comprising photoactivated benzyl or allyl 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 thermally activated methods. Pt(IV) materials such as cyclopentadienyltrimethylplatinum and 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 generally exhibit undesirable volatility, and reactions using these precatalysts tend to proceed slowly. Therefore, there is a need to discover precatalysts that enhance reactivity and exhibit favorable volatility characteristics. Summary of the Invention

[0002] This invention is a composition comprising: a) a compound functionalized with at least one Si-H group; b) a compound functionalized with at least one olefinic group; and c) a compound of formula 1.

[0003]

[0004] Formula 1

[0005] Where x is between 0 and 5; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, it is H, methyl, ethyl, or phenyl; and R 3 It is any of the following fragments:

[0006]

[0007] Each R 4 Independently H, C1-C6-alkyl; each R 5 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, aryl-(R 6 ) y Dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; each R 6 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; and each y is independently 0 to 5.

[0008] This invention addresses the need in the art by providing a non-volatile Pt(IV) precatalyst that rapidly decomposes into a catalytically active Pt(0) state under light irradiation. Detailed Implementation

[0009] This invention is a composition comprising: a) a compound functionalized with at least one Si-H group; b) a compound functionalized with at least one olefinic group; and c) a compound of formula 1.

[0010]

[0011] Formula 1

[0012] Where x is between 0 and 5; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, it is H, methyl, ethyl, or phenyl; and R 3 It is any of the following fragments:

[0013]

[0014] Each R 4 Independently H, C1-C6-alkyl; each R 5 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, aryl-(R 6 ) y Dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; each R 6 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; and each y is independently 0 to 5.

[0015] Compounds having at least one Si-H group preferably have at least two Si-H groups. Polyorganosiloxanes of Formula 2 are examples of such compounds:

[0016]

[0017] Formula 2

[0018] Each R' is independently C1-C6-alkyl, phenyl, or H; the sum of m + n is in the range of 2 or 3 to 400 or 200 or 3000 or 1000 or 500 or 100 or 50, and n is 0 or 2 or 3 to preferably 100 or 50 or 20; the condition being that when n is 0, each R' is H.

[0019] Compounds functionalized with at least one olefinic group are preferably functionalized with at least two terminal olefinic groups. Examples of such compounds include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene. Compounds functionalized with at least one olefinic group can also be Q-branched polyorganosiloxanes, as shown in Formula 3:

[0020]

[0021] Formula 3

[0022] Each R'' is represented by segment 1:

[0023]

[0024] Segment 1

[0025] The dashed lines represent the attachment points with oxygen atoms; each q is in the range of 0 or 2000 or up to 1000 or up to 500 or up to 250; each R a Independently C1-C6-alkyl or phenyl; and each R b For R a Or C2-C8 alkenyl groups; the condition is R b At least one of the groups is a C1-C6 alkenyl group. Preferably, each R a It is methyl, and R b At least one of the groups is a vinyl group.

[0026] Preferably, each R'' is represented by segment 2:

[0027]

[0028] Segment 2

[0029] An example of a Q-branched polyorganosiloxane is tetra(vinyldimethylsiloxy)silane (fragment 2b, where q = 0), commercially available from Gelest Inc. Q-branched polysiloxanes with q > 0 can be prepared by an acid-catalyzed equilibrium reaction of tetra(vinyldimethylsiloxy)silane with octamethylcyclotetrasiloxane at high temperature, followed by a neutralization step. The chain length (q) can be controlled by adjusting the relative amount of octamethylcyclotetrasiloxane.

[0030] Compounds functionalized with at least one olefin group can be linear polyorganosiloxanes having two terminal olefin groups, as shown in Formula 4:

[0031]

[0032] Formula 4

[0033] Where p is in the range of 0 or 2 or 10 or 40 or 50 to 3000 or 1000 or 500 or 250 or 150.

[0034] The compound having at least one olefinic group can also be a combination of polyorganosiloxanes of formula 3 and 4, wherein the weight / weight ratio of the polyorganosiloxane of formula 3 to the polyorganosiloxane of formula 4 is preferably in the range of 60:40 to 95:5.

[0035] Compounds functionalized with at least one olefinic group may also contain structural units of polyorganosiloxane resins, as shown in Formulas 5 and 6:

[0036]

[0037] Formula 5 Formula 6

[0038] Where R° represents methyl, ethyl, or phenyl, and the dashed line indicates the connection point with other groups.

[0039] In one embodiment of the invention, the molar:molar ratio of Si-H groups to olefin groups is in the range of 0.1:1 or 0.5:1 to 20:1 or 10:1 or 5:1 or 1.5:1.

[0040] US 4,510,094 (Drahnak, column 3, lines 33-44) reports the preparation of (η) according to the procedure of Robinson and Shaw by adding a solution of sodium cyclopentadienyl in THF to a solution of trimethylplatinum iodide in benzene. 5 -cyclopentadienyl)trimethylplatinum ((Cp)trimethylplatinum) complex (J. Chem, Soc. 1965, 1529). Furthermore, Drahnak cites (Cp)dimethylbenzylplatinum (column 4, line 58, (Cp)Me2BzPt) as a representative compound of this invention; however, details of its preparation are not disclosed; therefore, the inventors could not prepare (Cp)Me2BzPt and its analogues without extensive experiments taught or implied by Drahnak. It has now been found that compounds of Formula 1 can be 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 is contacted with alkali metal bis(tetramethylsilyl)amides such as potassium or sodium bis(tetramethylsilyl)amino, or with alkyl lithium such as n-butyllithium, to form (R 1 ) x -Cp alkali metal salts (intermediate A):

[0041]

[0042] In a separate series of steps, a toluene-functionalized Grignard reagent, such as (o-tolyl)magnesium bromide, can be contacted with a halide-functionalized dimethyl(vinyl)silyl compound, such as dimethyl(vinyl)chlorosilane, to form a toluene-functionalized dimethyl(vinyl)silyl compound. This compound can then be treated with a brominating agent, such as N-bromosuccinimide (NBS), in the presence of a radical initiator, such as azobisisobutyronitrile (AIBN), to generate a dimethyl(vinyl)silyl-functionalized bromomethylbenzene BrCH2-phenyl-SiMe2Vi.

[0043]

[0044] 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 metal salts.

[0045] Where R 3 phenyl-(R 5 ) y The compound of formula 1 can be prepared as follows: norbornene diene dimethyl platinum(II) (NBD)PtMe2 is dissolved in a suitable donor solvent such as pyridine, and then reacted with benzyl bromide (e.g., Br-C(R)). 2 )2phenyl(R 5 ) y The mixture is contacted with intermediate A in the same reaction vessel, wherein y is 0 to 5, preferably 1, 2 or 3, to form the compound of the present invention.

[0046]

[0047] Each R 1 Preferably, each R is independently C1-C4-alkyl or phenyl; 2 Preferably, H. In one embodiment, each R 5 Independently methyl, trifluoromethyl, nitro, but-3-en-1-yl, methoxy, or aryl-(R 6 ) y The aryl group is phenyl, naphthyl, or anthracene.

[0048] Specific examples of compounds according to this embodiment of the invention include the following:

[0049]

[0050] The compounds of the present invention, wherein R 3 For substituted or unsubstituted alkenyl groups, similar preparation can be achieved by contacting a mixture of (NBD)PtMe2 / pyridine with a brominated alkene such as 1-bromo-3-methylbut-2-ene under similar reaction conditions to form the following compounds:

[0051]

[0052] Each R 1 Preferably, each R is independently C1-C4-alkyl or phenyl; and each R 2 H is preferred.

[0053] The compound of Formula 1 is a Pt(IV) precatalyst that exhibits excellent efficiency in promoting UV-triggered hydrosilylation chemistry. The relatively low vapor pressure of the precatalyst is also advantageous, as the amount of precatalyst required to initiate hydrosilylation is lower due to its reduced volatility.

[0054] Example

[0055] In the following examples, Cp refers to the unsubstituted cyclopentadiene ring, and Cp* refers to the pentamethyl-substituted cyclopentadiene ring. Me Cp refers to a monomethyl-substituted cyclopentadienyl ring, 2,6-Me2Bz refers to 2,6-dimethylbenzyl, 4-CF3Bz refers to 4-trifluoromethylbenzyl, 3-Me-2-Bu refers to 3-methylbut-2-enyl, 2-BuBz refers to 2-(but-3-en-1-yl)benzyl, 2-PhBz refers to 2-phenylbenzyl, and 2-SiMe2ViBz refers to 2-dimethyl(vinyl)silyl.

[0056] Intermediate Example 1 - Preparation of (NBD)PtMe2

[0057] (NBD)PtMe2 was prepared using a modified procedure derived from 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.

[0058] Intermediate Example 2 - Preparation of 1-(bromomethyl)-2-(but-3-en-1-yl)benzene

[0059] In a nitrogen-filled glove box, 1,2-bis(bromomethyl)benzene (8.00 g, 30.31 mmol, 1 equivalent) was placed in a 250 mL wide-mouth glass flask 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 28.8 mL (28.8 mmol, 0.95 equivalent) of a 1.0 M solution of allyl magnesium bromide in diethyl ether was added dropwise. The resulting gray suspension was warmed to ambient temperature and stirred vigorously for 4 hours. The reaction mixture was then removed from the glove box and diluted with deionized water (25 mL). 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, concentrated on silica gel, and purified by column chromatography using 100% hexane as the mobile phase. Fractions 3-5 were combined and concentrated to a colorless liquid. Yield: 2.33g, 34.0%. 1 ¹H NMR (400MHz, C6D6) δ 7.06 – 6.94 (m, 2H), 6.90 (t, J = 7.4Hz, 2H), 5.72 (ddt, J = 16.9, 10.2, 6.6Hz, 1H), 5.05 – 4.85 (overlapping resonance, 2H), 4.12 (s, 2H), 2.68 – 2.56 (m, 2H), 2.31 – 2.13 (m, 2H). 13 C NMR (101MHz, C6D6) δ 140.90, 137.95, 135.88, 130.87, 129.91, 129.06, 126.70, 115.35, 34.95, 31.82, 31.65.

[0060] Intermediate Example 3: Preparation of dimethyl(o-tolyl)(vinyl)silane

[0061] Dichloromethyl(vinyl)silane (4.00 g, 33.15 mmol, 1 equivalent) was placed in a 150 mL wide-mouth glass flask with THF (75 mL) and a magnetic stir bar. The colorless solution was stored at -25 °C for 1 hour. Once cooled, a 2.0 M solution of o-tolyl magnesium bromide in THF (16.58 mL, 33.15 mmol, 1 equivalent) was slowly added. The reaction mixture was then slowly warmed to ambient temperature and stirred for 24 hours. A portion (20 mL) of 1,4-dioxane was then added to the reaction mixture. The resulting suspension was stirred at ambient temperature for 1 hour and then passed through a diatomaceous earth pad on top of a disposable PTFE cartridge filter. The pale yellow filtrate was concentrated under vacuum to give a pale yellow residue. The residue was extracted into hexane (40 mL) and filtered successively through 0.45 μm and 0.20 μm PTFE syringe filters to give a pale yellow solution. The solution was stored at -25 °C for 48 hours, which caused a colorless solid to precipitate. The solid was filtered off using a 0.20 μm PTFE syringe filter. The filtrate was concentrated into a pale yellow liquid. Yield: 3.95 g, 67.6%. 1 H NMR (400MHz, C6D6) δ 7.52 (dd, J = 7.3, 1.6Hz, 1H), 7.22 – 7.14 (m, 1H), 7.10 (t, J = 7.3Hz, 1H), 7.04 (d, J = 7.5Hz, 1H), 6.30 (dd, J = 20.3, 14.6Hz, 1H), 5.95 (dd, J = 14.6, 3.7Hz, 1H), 5.69 (dd, J = 20.3, 3.7Hz, 1H), 2.33 (s, 3H), 0.33 (s, 6H). 13 C NMR (101MHz, C6D6) δ 143.97, 139.06, 136.47, 135.33, 132.39, 130.18, 129.83, 125.41, 23.24, -1.84.

[0062] Intermediate Example 4 - Preparation of (2-(bromomethyl)phenyl)dimethyl(vinyl)silane

[0063] Dimethyl(o-tolyl)(vinyl)silane (3.00 g, 17.01 mmol, 1 equivalent) was placed in a 150 mL wide-mouth glass flask with ethyl deoxyethyl acetate (75 mL, previously dried on a molecular sieve), NBS (3.03 g, 17.01 mmol, 1 equivalent), AIBN (0.559 g, 3.40 mmol, 0.2 equivalent), and a magnetic stir bar. The reaction mixture was then heated at 70 °C for 18 hours. After cooling to ambient temperature, the reaction mixture was filtered through a diatomaceous earth pad on top of a disposable PTFE cartridge filter. The pad was washed with hexane (2 x 15 mL). The combined washes and filtrates were then concentrated onto silica gel and purified by ISCO chromatography in the mobile phase using 100% hexane. The desired product was separated from fractions 3–9. Yield: 1.12 g, 25.8%. 1 H NMR (500MHz, C6D6) δ 7.38 (dd, J = 7.5, 1.5Hz, 1H), 7.22 (dd, J = 7.6, 1.3Hz, 1H), 7.07 (td, J = 7.5, 1.5Hz, 1H), 7.00 (td, J = 7.4, 1.3Hz, 1H), 6.33 – 6.22 (m, 1H), 5.97 – 5.87 (m, 1H), 5.66 (dd, J = 20.3, 3.5Hz, 1H), 4.38 (s, 2H), 0.33 (s, 6H). 13 C6D6 NMR (126MHz, C6D6) δ 143.96, 138.62, 137.35, 135.60, 133.06, 131.46, 130.18, peaks masked by NMR solvent, 34.58, -1.46.

[0064] Intermediate Example 5 - Preparation of CpPtMe2(2,6-Me2Bz)

[0065] (NBD)PtMe2 (84 mg, 0.265 mmol) and pyridine (3 mL) were placed in a vial equipped with a magnetic stir bar. The mixture was stirred at room temperature for 1 hour in a nitrogen-filled glove box. Then, 2,6-dimethylbenzyl bromide (Me2BzBr, 53 mg, 0.265 mmol) was added to the vial, and the solution was stirred for 1 hour. An additional 15 mg of Me2BzBr was added to the vial, and stirring continued overnight. An additional 15 mg of Me2BzBr was added, and the mixture was heated to 45°C and stirred overnight. NaCp solution (2.4 M, in THF, 110 μL, 0.265 mmol) was added to the mixture, and stirring continued for 2 hours at room temperature. The mixture was then heated to 45°C and stirred overnight. The mixture was dried under vacuum, Et2O was added, and the mixture was filtered through a syringe filter and dried under vacuum. The red residue was then absorbed in CH2Cl2 and passed through a Florisil pad. The filtrate was collected and dried to give a red solid (43 mg, 39%). 1 H NMR (400MHz, C6D6) δ 6.94 (m, 3H, Ar), 4.81 (m, 5H, Cp), 2.67 (m, 2H, Pt-CH2, 96Hz), 2.26 (m, 6H, Me), 1.27 (m, 6H, Pt-CH3, 82Hz); 13 C NMR (101MHz, C6D6) δ 150.74, 134.55, 124.78, 97.91, 20.28, 9.89 ( 1 J Pt-C =678Hz), -18.85 ( 1 J Pt-C = 724Hz); 195 Pt NMR (85MHz, C6D6) δ -5009.62.

[0066] Intermediate Example 6 - Preparation of Cp*PtMe2(4-CF3Bz)

[0067] (NBD)PtMe2 (60 mg, 0.189 mmol) and pyridine (5 mL) were combined in a 20 mL vial equipped with a magnetic stir bar and stirred for 10 min in a nitrogen-filled glove box. Then, 4-trifluoromethylbenzyl bromide (45 mg, 0.189 mmol) was added to the mixture, and stirring continued for 1.5 h, followed by the addition of LiCp* (34 mg, 2.36 mmol). The mixture was heated to 45 °C and stirred overnight. The red mixture was dried under vacuum, and then CH2Cl2 was added; the resulting solution was filtered through a Florisil pad, and the pale yellow filtrate was concentrated under vacuum to give 80 mg (82%) of the title compound as a yellow oil.1 H NMR (C6D6, 400MHz) δ 7.36 (d, 2H, Ar), 6.97 (d, 2H, Ar), 2.79 (pt, 2H, CH2, 2 J Pt-H =84Hz), 1.20 (s, 15H, Cp*), 0.69 (pt, 6H, Pt-CH3, 2 J Pt-H = 60Hz); 13 C NMR (δ 100MHz) 153.50, 125.78 (q), 125.68 (q), 124.84 (m), 102.68, 11.31 ( 1 J Pt-C = 667Hz), 7.25, -6.24 ( 1 J Pt-C = 730Hz); 19 F NMR (471MHz, C6D6) δ -61.52; 195 Pt NMR (85.5MHz) delta -5060.66.

[0068] Intermediate Example 7 - Preparation of Cp*PtMe2(3-Me-2-Bu)

[0069] (NBD)PtMe2 (67 mg, 0.211 mmol) and pyridine (5 mL) were transferred to a 20 mL vial equipped with a stir bar and stirred for 10 min in a nitrogen-filled glove box. Then, isopentenyl bromide (25 μL, 0.211 mmol) was added, and the mixture was stirred for 1.5 h, followed by the addition of LiCp* (39 mg, 0.275 mmol). The mixture was heated to 45 °C and stirred overnight. The red mixture was dried under vacuum, CH2Cl2 was added, and the mixture was filtered through a Florisil pad. The pale yellow filtrate was concentrated under vacuum to give 65 mg (72%) of the title compound as a yellow oil. 1 H NMR (C6D6, 400MHz): δ 5.37 (m, 1H, CH), 2.41 (ptd, 2H, CH2, 2 J Pt-H = 100Hz, 2 J H-H = 12Hz), 1.79 (m, 3H, CH3), 1.74 (m, 3H, CH3), 1.52 (m, 15H, Cp*), 0.77 (pt, 6H, Pt-CH3, 2 J Pt-H = 80Hz); 13C NMR (C6D6, 100MHz) δ130.18, 125.44, 102.51, 26.09, 18.65, 7.82, 6.85, -8.17; 195 Pt NMR (C6D6, 85.5MHz) delta -5073.39.

[0070] Intermediate Example 8 - Me Preparation of CpPtMe2(2-BuBz)

[0071] (NBD)PtMe2 (0.118 g, 0.37 mmol, 1 equivalent) and pyridine (3 mL) were transferred to a 20 mL vial equipped with a magnetic stir bar and stirred at ambient temperature for 20 minutes in a nitrogen glove box. 1-(bromomethyl)-2-(but-3-en-1-yl)benzene (0.084 g, 0.37 mmol, 1 equivalent) was added dropwise, followed by pyridine (1 mL), ensuring quantitative transfer of reagents to the reaction vial. After stirring at ambient temperature for 4 hours, Li was added at ambient temperature. Me Cp (0.038 g, 0.45 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 passed through a diatomaceous earth pad and a 0.45 μm PTFE syringe filter. The diatomaceous earth pad was washed with hexane (2 x 3 mL), and the washes were combined with the filtrate. Volatiles were then removed under vacuum, and the purple residue was stored at -25 °C for 18 hours. The residue was then milled with hexane (2 x 2 mL), extracted into hexane (2 x 10 mL), and passed through a Fluorisil pad and two sequential 0.20 μm PTFE syringe filters. The filtrate was then concentrated under vacuum to give a pale yellow liquid. The liquid was finally extracted into hexane (6 mL), passed through a Fluorisil pad and a 0.20 μm PTFE syringe filter, and concentrated under vacuum to a nearly colorless liquid. Yield: 0.110 g, 65.8%. 1 ¹H NMR (500MHz, C6D6) δ 7.29 – 7.20 (m, 1H), 7.10 – 6.91 (overlapping resonance, 3H), 5.92 (ddt, J = 16.9, 10.2, 6.6Hz, 1H), 5.11 (dq, J = 17.0, 1.7Hz, 1H), 5.01 (ddt, J = 9.2, 2.2, 1.1Hz, 1H), 4.82 (t, J = 2.1Hz, 2H), 4.60 (t, J = 2.4Hz, 2H), 3.02 (m, 2 J Pt-H= 97.6Hz, 2H), 2.86 – 2.67 (m, 2H), 2.49 – 2.35 (m, 2H), 1.52 (m,J Pt-H = 6.3Hz, 3H), 1.18 (m, 2 J Pt-H = 81.2Hz, 6H). 13 C NMR (101MHz, C6D6) δ 150.50 (J Pt-C = 60.9Hz), 138.93, 137.71 (J Pt-C = 22.7Hz), 129.87 (J) Pt-C = 22.0Hz), 129.17 (J) Pt-C =14.7Hz), 126.18 (J) Pt-C = 14.7Hz), 125.01 (J) Pt-C = 15.8Hz), 114.90, 114.44, 98.90, 93.41, 35.57, 33.01, 11.43, 9.99 ( 1 J Pt-C = 675.3Hz), -14.74 ( 1 J Pt-C = 732.1Hz). 195 Pt NMR (86MHz, C6D6) δ -4986.46.

[0072] Intermediate Example 9 - Me Preparation of CpPtMe2(2-PhBz)

[0073] (NBD)PtMe2 (0.143 g, 0.45 mmol, 1 equivalent) was placed in a 30 mL glass vial with pyridine (2 mL) and a magnetic stir bar. The resulting pale yellow solution was stirred at ambient temperature for 20 minutes, and then 2-(bromomethyl)-1,1'-biphenyl (0.111 g, 0.45 mmol, 1 equivalent) was added directly in solid form. 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. MeCp (0.047 g, 0.54 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. This extraction and filtration was repeated twice. The combined pale yellow filtrate was then concentrated under vacuum to give a yellow liquid, which was stored overnight at -25 °C. The material was extracted again into hexane (6 mL) and filtered again through a Florisil pad and a 0.20 μm PTFE syringe filter. The solution was then concentrated to a nearly colorless, viscous liquid. Yield: 0.111 g, 52.2%. 1 ¹H NMR (400MHz, C6D6) δ 7.45 – 7.36 (overlapping resonance, 3H), 7.28 – 7.20 (overlapping resonance, 2H), 7.19 – 7.12 (overlapping resonance, 2H), 7.10 (td, J = 7.5, 1.6Hz, 1H), 7.01 (td, J = 7.4, 1.5Hz, 1H), 4.83 – 4.73 (m, 2H), 4.60 – 4.51 (m, 2H), 3.29 (m, 2 J Pt-H =102.1Hz, 2H), 1.49 (m, J) Pt-H = 6.3Hz, 3H), 0.95 (m, 2 J Pt-H = 81.4Hz, 6H). 13 C NMR (101MHz, C6D6) δ 149.72 (J Pt-C = 59.1Hz), 143.29, 140.04 (J Pt-C = 25.0Hz), 130.90, 130.60 (J Pt-C = 15.4Hz), 130.14 (J) Pt-C = 4.1Hz), 127.29 (J) Pt-C = 14.6Hz), 126.91, 124.77 (J Pt-C = 16.1Hz), 114.87 (J) Pt-C = 15.6Hz), 98.69, 92.69, 11.42, 8.72 ( 1 J Pt-C =678.6Hz), -14.73 ( 1 JPt-C = 732.0Hz). 195 Pt NMR (85MHz, C6D6) δ -4984.80.

[0074] Intermediate Example 10 - Me Preparation of CpPtMe2(2-SiMe2ViBz)

[0075] (NBD)PtMe2 (0.123 g, 0.39 mmol, 1 equivalent) was placed in a 30 mL glass vial with pyridine (2 mL) and a magnetic stir bar. The resulting pale yellow solution was stirred at ambient temperature for 20 minutes, and then ((2-bromomethyl)phenyl)dimethyl(vinyl)silane (0.087 g, 0.39 mmol, 1 equivalent) was added dropwise. Then, additional pyridine (1 mL) was added. After stirring for a total of 2 hours, Li was added at ambient temperature. Me Cp (0.040 g, 0.47 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 extraction and filtration were repeated twice. The combined yellow filtrate was then concentrated under vacuum to give an orange liquid, which was stored overnight at -25 °C. The material was extracted again into hexane (6 mL) and filtered again 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 thick yellow liquid. Yield: 0.082 g, 44.1%. 1 ¹H NMR (400MHz, C6D6) δ 7.49 – 7.37 (overlapping resonance, 2H), 7.15 – 7.11 (m, 1H), 6.99 (tt, J = 8.2, 2.8Hz, 1H), 6.49 (dd, J = 20.3, 14.6Hz, 1H), 6.01 (dd, J = 14.6, 3.6Hz, 1H), 5.80 (dd, J = 20.3, 3.7Hz, 1H), 4.84 (t, J = 2.2Hz, 2H), 4.65 (t, J = 2.3Hz, 2H), 3.23 (m, 2 J Pt-H = 96.0Hz, 2H), 1.53 (m, J) Pt-H = 6.0Hz, 3H), 1.22 (m, 2 J Pt-H = 80.8Hz, 6H), 0.47 (s, 6H).13 C NMR (101MHz, C6D6) δ 158.73 (J Pt-C = 60.3Hz), 140.03, 135.00 (J Pt-C = 10.3Hz), 132.93, 131.90, 130.90 (J Pt-C = 23.6Hz), 129.32 (J) Pt-C = 12.1Hz), 124.16 (J) Pt-C = 13.6Hz), 114.85 (J) Pt-C = 15.4Hz), 99.21, 93.46, 15.62 ( 1 J Pt-C = 688.3Hz), 11.43, -1.11, -14.87 ( 1 J Pt-C = 730.6Hz). 195 Pt NMR (85MHz, C6D6) δ -4981.10.

[0076] Intermediates 5-10 (pre-catalyst) 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 intermediate Example 5; formulation 2 uses the compound of intermediate Example 6, and so on. 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 weight % concentration.

[0077] Table 1 - Polyorganosiloxane Formulations

[0078]

[0079] Gelation point determination

[0080] 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.

[0081] Table 2 - Gelation Point Time of Formulations

[0082]

[0083] The formulations of the present invention exhibit excellent reactivity, as demonstrated by a gel point time of <30 minutes.

Claims

1. A composition comprising: a) a compound functionalized with at least one Si-H group; b) a compound functionalized with at least one olefinic group; and c) a compound of formula 1: Formula 1 Where x is between 0 and 5; each R 1 Independently C1-C6-alkyl or phenyl; each R 2 Independently, it is H, methyl, ethyl, or phenyl; and R 3 It is any of the following fragments: Each R 4 Independently H, C1-C6-alkyl; each R 5 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, aryl-(R 6 ) y Dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; each R 6 Independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halogen, dimethyl (vinyl)silyl or C2-C 12 -Alkenyl; and each y is independently 0 to 5.

2. The composition according to claim 1, wherein the compound functionalized with at least one Si-H group is a polyorganosiloxane functionalized with at least two Si-H groups and having a degree of polymerization in the range of 2 to 400; and the compound functionalized with at least one olefin group is a polyorganosiloxane functionalized with at least two vinyl groups and having a degree of polymerization of up to 1000.

3. The composition according to claim 2, wherein each R 1 Independently C1-C4-alkyl or phenyl; each R 2 For H; and R 3 Represented by the following fragment: Each R 5 Independently methyl, methoxy, trifluoromethyl, but-3-en-1-yl, phenyl-(R 6 ) y Dimethyl (vinyl)silyl or nitro; each R 6 It is methyl, methoxy, trifluoromethyl, dimethyl(vinyl)silyl, but-3-en-1-yl or nitro; and each y is independently 0, 1, 2 or 3.

4. The composition according to claim 3, wherein the compound of formula 1 is selected from: 。 5. The composition according to claim 2, wherein each R 1 Independently C1-C4-alkyl or phenyl; each R 2 For H; and for each R 3 For the following segment: 。 6. The composition according to claim 5, wherein the compound of formula 1 is represented by the following compound: 。

Images