New Vinylgermanium Derivatives of Silsesquioxanes and Their

Aug 3, 2015 - New vinylgermanium cubic derivatives of silsesquioxanes (i.e., monovinylhepta(alkyl, phenyl)germasilsesqiuoxanes and ...
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New Vinylgermanium Derivatives of Silsesquioxanes and Their Ruthenium ComplexesSynthesis, Structure, and Reactivity Dawid Frąckowiak,† Patrycja Ż ak,† Grzegorz Spólnik,‡ Mikołaj Pyziak,† and Bogdan Marciniec*,†,†† †

Adam Mickiewicz University in Poznan, Faculty of Chemistry, Umultowska 89b, 61-614 Poznan, Poland Adam Mickiewicz University, Centre for Advanced Technologies, Umultowska 89c, 61-614 Poznan, Poland ‡ Institute of Organic Chemistry PAS, M. Kasprzaka 44/52, 01-224 Warsaw, Poland ††

S Supporting Information *

ABSTRACT: New vinylgermanium cubic derivatives of silsesquioxanes (i.e., monovinylhepta(alkyl, phenyl)germasilsesqiuoxanes and (dimethylvinylgermoxy)heptaisobutylsilsesquioxanes) were synthesized and characterized by spectroscopic methods. The first ruthenium− germasilsesquioxyl complexes were also prepared via stoichiometric reaction of RuHCl(CO)(PPh3)3 with the abovementioned vinylgermanium derivatives of silsesquioxanes, and their structures were determined by spectroscopic and X-ray analyses. The initial ruthenium complex as well as the above-mentioned Ge−Ru complexes were tested as catalysts, in the germylative coupling with olefins, and proved to be active in the case of (dimethylvinyl)germoxyheptaisobutylsilsesquioxane but showed no activity toward vinylgermasilsesquioxanes. A general mechanism for the germylative coupling of the two vinylgermanium derivatives of silsesquioxanes is presented.

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INTRODUCTION Polyhedral oligomeric silsesquioxanes (POSS) represent an unique class of organosilicon compounds sharing features of both inorganic and organic materials. Cubic silsesquioxanes and their derivatives (Chart 1A) gained vast interest because of

On the other hand, reports on germasilsesquioxanes (Chart 1B) are scarce. Feher et al. provided the synthesis and NMR data for only one cubic germasilsesquioxane containing methylsubstituted germanium atom.4 Germasilsesquioxanes were also the subject of theoretical calculations5 and experiments involving hydrogen/deuterium trapping inside of the POSS cage.6 Recently, Bauzá et al. reported theoretical calculations on tetrel-bonding interactions in germasilsesquioxane cage.7 There has also been no report on the synthesis of germoxy-substituted silsesquioxanes. For the last 20 years, we have developed the catalytic coupling of olefins with vinylmetalloids (Si, Ge, B), which occurs in the presence of transition metal complexes containing MH or ME bonds (where M = Ru, Rh, Ir) and yields unsaturated organometalloid derivatives and ethylene by the cleavage of C−H bond of the olefin and E-C bond of the vinylmetalloid (Scheme 1), for review see ref 8. This paper reports the synthesis of the first vinyl-substituted germanium POSS derivatives and their reactivity in the germylative coupling with styrene catalyzed by RuHCl(CO)(PCy3)2 per analogy to our previous study of the silylative coupling of olefins with vinylsilsesquioxanes. The latter reaction proved to be efficient and stereoselective protocol for the functionalization of a variety of alkenyl-substituted silsesquioxanes (i.e., heptaisobutylvinylsilsesquioxane,9a octavinylsilsesquioxane,10,11 and vinylspherosilicates).12 This study also

Chart 1. General Structure of Cubic Silsesquioxane and Germasilsesquioxane

their great stability, straightforward preparation, and versatile applications (e.g., as molecular models of heterogeneous catalysts, components of nanocomposites, materials for the synthesis of optoelectronic and biomedical devices; for review, see refs 1,2). Considerable interest has arisen in so-called heterosilsesquioxanes containing other heteroatoms incorporated into the POSS cage (e.g., Ge, Sn, Al, B, P, transition metal, etc.), which are studied as potential molecular models for heterogeneous catalysts and for the synthesis of new advanced materials.1,3 © XXXX American Chemical Society

Received: February 26, 2015

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DOI: 10.1021/acs.organomet.5b00142 Organometallics XXXX, XXX, XXX−XXX

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Organometallics Scheme 1. General Mechanism for the Catalytic TransMetallation Reaction

Scheme 4. Synthesis of (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane

allowed us to synthesize and characterize the first Ru−Si silsesquioxyl complexes as the active intermediates in the above-mentioned reaction.9b

and 29 Si NMR spectroscopy as well as ASAP mass spectrometry. Chlorodimethylvinylgermane 6, which is not a commercially available reagent, was prepared by a new procedure. The synthetic protocol described in literature consists of three steps with the use of dimethylamine and chlorodiphenylphosphine.14 We found this method rather inconvenient for a small-scale synthesis (up to 5 g). Our aim was to prepare 6 in one step by transmetalation reaction of dichlorodimethylgermane with tributylvinylstannane (Scheme 5), a task which proved to be

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RESULTS AND DISCUSSION Vinylgermasilsesquioxanes were prepared by a corner-capping reaction of respective POSS silanetriols 2a−e with trichlorovinylgermane 1 (Scheme 2).

Scheme 5. One-Step Synthesis of Chlorodimethylvinylgermane

Scheme 2. General Synthesis of Vinylgermasilsesquioxanes difficult. The reactivity of halogermanes toward exchange of chlorine atoms with vinyl group decreases with increasing number of alkyl substituents, which is reflected in harsh reaction conditions needed to reach a full conversion of dichlorodimethylgermane to 6. Only after 2 weeks of heating dichlorodimethylgermane with a large excess of tributylvinylstannane in the presence of ABCN at 150 °C, we were able to isolate pure 6 in 75% yield by careful trap-to-trap distillation of the reaction mixture. Detailed discussion regarding the synthesis of all the substrates is presented in the Experimental Section. When a toluene solution of the ruthenium hydride complex [RuHCl(CO)(PPh3)3] was heated in the presence of 1 equiv. of 3b at 120 °C, the color of the solution gradually turned orange within 24 h. The 1H NMR spectrum of the postreaction mixture revealed disappearance of signals at δ = −6.60 (dt) ppm characteristic of the Ru−H bond, and formation of a new singlet at δ = 5.25 ppm which can be assigned to ethylene. Moreover, the appearance of a new singlet at δ = 37.47 ppm was observed in the 31P{1H} NMR spectrum. On the basis of these observations, we synthesized ruthenium complexes of other vinylgermasilsesquioxanes (7a−e) (Scheme 6), which were isolated in high yields as canary yellow powders. All complexes proved to be extremely stable toward air and moisture. Structures of complexes 7a, 7b, 7c and 7d (Figure 1) were confirmed via X-ray analysis. The crystals were obtained by slow evaporation of hexane solution. Especially, 7b gave a large number of beautiful orange crystals (picture included in Supporting Information). The ruthenium atom is 5-coordinated in a square pyramidal fashion, with germanium at its apex and phosphines at the opposite base corners. The square pyramid is slightly distorted, with the Ge−Ru−PPh3 angle varying between 95 and 100°. In

Compound 1 was easily obtained in the slightly modified variant of the well-known redistribution reaction of GeCl4 with tributylvinylstannane in the presence of radical initiator (Scheme 3).13 Scheme 3. Synthesis of Trichlorovinylgermane

Dropwise addition of 1 to the solution of 2a−d and triethylamine in THF and subsequent stirring for 24 h, after which the mixture was filtered off from ammonium salts, afforded crude products as white powders. All germasilsesquioxanes 3a−d were purified by precipitation in methanol− water mixture and thoroughly dried. (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane 5, which is an analogue of wellknown silyl derivative, was synthesized in high yield by condensation of monosilanolisobutyl POSS 4 with chlorodimethylvinylgermane 6 in the presence of triethylamine (Scheme 4) and purified in the same manner as vinylgermasilsesquioxanes. Pure products (obtained as white, microcrystalline powders in excellent yields) were fully characterized by 1H, 13C{1H}, B

DOI: 10.1021/acs.organomet.5b00142 Organometallics XXXX, XXX, XXX−XXX

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Organometallics Scheme 6. Synthesis of Germasilsesquioxane Ruthenium Complexes

general, the size of groups attached to GeSi7O12 moiety does not influence Ru−PPh3 distances, but Ge−Ru−PPh3 angle increases along with their size. Ruthenium−chlorine distance varies between 2.41 and 2.47 Å, and Ge−Ru−Cl angle between 94° and 105°. Carbonyl ligands are near the pyramid plane, with distances from the central atom varying between 1.66 and 1.80 Å. Carbonyl and chlorine ligands are highly interchangeable (cf. experimental part), effecting in lower positional certainty and higher standard deviations of geometrical measurements concerning them. The GeSi7O12 cage is distorted around germanium atom, with Ge−O bonds being 0.15 Å longer than Si−O bonds and, which is worth noting, Ge−O−Si angles being significantly larger near the position of the CO/Cl ligands (O3 oxygen atom): the angles change from the standard 141−144° range to around 165° in all three cases. At the same time, the adjacent carbonyl C−O bond elongates by 0.15 Å, and the Ge−O bond length shortens by 0.02 Å. The same angle change, although less acute, could be noted in the previously described complex9b containing the Si8O12 moiety (shift to around 160°). Unlike in the Si8O12 moiety, the Si−O− Si angles vary significantly and take values from 138° up to 158°. Also, in this case, three oxygen atoms at the side opposite to ruthenium do not differ from others by distances nor angles. Selected bond lengths and angles are gathered in Table 1. A ruthenium complex 8 was also obtained (Scheme 7); its synthesis was performed in a manner similar to 7a−e. As we previously demonstrated for the silylative coupling mechanism of vinylsilsesquioxanes with olefins, complexes 7a− e and 8 can be treated as intermediates in the catalytic cycle. In order to study the reactivity of vinylgermasilsesquioxanes in germylative coupling with styrene, an equimolar reaction between ruthenium-germasilsesquioxane complex 7b and styrene was performed. After 24 h, the 1H NMR examination showed that in equimolar reaction, only a trace amount of Ru− Ge complex was converted to styrylgermasilsesquioxane. We examined each synthesized vinylgermasilsesquioxane in catalytic tests under various conditions to no avail. Regardless of substituent type in the germasilsesquioxane cage, reaction temperature, use of additives (CuCl, but also CuI and CuCN), and styrene−germasilsesquioxane molar ratio, we were unable to obtain even traces of the coupling product. Even higher molar ratio of the catalyst (up to 5% mol) and reversed order of applying the substrates did not allow us to detect the products of coupling reaction. On the other hand, the stoichiometric reaction of 8 with styrene gave full conversion of Ru−Ge complex to styryl substituted compound (Scheme 8). Trans-germylation of 5 with styrene proceeded smoothly at 140 °C in the presence of 1% mol catalyst as an additive, giving only a single product 9a; we also obtained other styrylsubstituted derivatives (Scheme 9 and Table 1).

Figure 1. Crystal structures of the complexes 7a−d. Atomic displacement parameters drawn at 50% probability for all atoms, except for hydrogen atoms and few selected hydrocarbon moieties, drawn as ball-and-stick in order to improve figure clarity. C

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Organometallics Table 1. Selected Bond Lengths and Angles for 7a−d 7a

7b

7c

7d

166.6(3) 146.8(6) 95.3(2) 104.8(1) 87.9(6) 90.3(9) 99.9(5) 98.1(5)

163.2(2) 145.3(2) 95.8(1) 102.7(1) 88.7(6) 88.1(5) 98.26(4) 99.42(4)

1.756(4) 1.780(3) 2.471(8) 2.394(5) 1.720(2) 1.720(3) 1.260(2) 1.120(4) 2.370(2) 2.247(2) 2.3501(9)

1.768(3) 1.777(3) 2.421(5) 2.386(4) 1.80(2) 1.80(2) 1.13(3) 1.17(2) 2.354(1) 2.362(1) 2.3440(7)

bond angles Ge−O03−Si3 other Ge−O−Si and Si−O−Si avg. Ge−Ru−Cl a Ge−Ru−Cl b Ge−Ru−C (CO) a Ge−Ru−C (CO) b Ge−Ru−P1 Ge−Ru−P2 Ge−O03 other Ge−O avg. Ru−Cl a Ru−Cl b Ru−C (CO) a Ru−C (CO) b C−O (CO) a C−O (CO) b Ru−P1 Ru−P2 Ru−Ge

164.7(1) 148.0(3) 94.0(5) 98.0(5) 88.7(2) 90.8(2) 98.3(2) 95.3(2)

164.1(2) 148.0(5) 99.8(1) 105.9(1) 88.4(3) 91.2(5) 96.2(3) 96.4(3) interatomic distances 1.753(2) 1.754(3) 1.773(2) 1.767(2) 2.413(2) 2.438(5) 2.428(2) 2.414(4) 1.202(8) 1.660(8) 1.755(7) 1.730(1) 1.150(1) 1.290(1) 1.202(8) 1.090(3) 2.3865(7) 2.370(1) 2.3573(7) 2.394(1) 2.3473(7) 2.3486(5)

elimination, a styryl derivative was formed in the process. It appears clearly that transfer of vinyl-substituted germanium atom from the silsesquioxane framework to the side chain results in a significant change in reactivity of Ge−Ru complex, which can also be seen in the relative ease of homocoupling of 5.

Scheme 7. Synthesis of Complex 8

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CONCLUSIONS New cubic monovinyl(heptaalkyl or phenyl)germasilsesquioxanes and (dimethylvinylgermoxy)heptaisobutylsilsesquioxane were synthesized, and their structures were determined by spectroscopic methods. The first ruthenium−germanium complexes of POSS were also prepared via the reactions of RuHCl(CO)(PPh3)3 with vinylgermanium POSS derivatives, and their structures were characterized by the spectroscopic and X-ray methods. Stoichiometric study of insertion of styrene into the Rugermanium bond in the above complexes as well as respective catalytic measurements of the germylative coupling of styrenes catalyzed by the initial complex RuHCl(CO)(PPh3)3 confirmed the high activity of vinylgermoxy derivatives of POSS and no activation in the case of cubic vinylgermasilsesquioxanes. A general mechanistic scheme for catalysis reflecting the results of the stoichiometric and catalytic study has been finally presented.

Scheme 8. Stoichiometric Reaction of Complex 8 with Styrene

We were also able to obtain the product of homocoupling reaction 10 in 85% yield (not isolated; yield was determined by 1 H NMR analysis) (Scheme 10) On the basis of both catalytic and stoichiometric reactions, we propose a general mechanism for the reaction of new vinylgermanium POSS derivatives (Scheme 11). Vinylgermasilsesquioxanes 3a−e undergo insertion into Ru−H bond with subsequent β-elimination of the ethylene molecule and formation of Ru−Ge complexes 7a−e. These complexes are no further catalytically active toward the insertion of styrene, which was only achieved in the stoichiometric process, though only trace amounts of the coupled product were formed. This fact illustrates the unusual stability of Ru−Ge species. (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane 5 followed a similar reaction pattern as vinylgermasilsesquioxanes and formed the Ru−Ge species 8, which in contrast to 7a−e, proved to be active toward the insertion of styrene. After the β-

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EXPERIMENTAL SECTION

1. General Methods and Chemicals. Unless mentioned otherwise, all operations were performed by using standard Schlenk techniques. 1H and 13C{1H} NMR spectra were recorded on a Varian 400 operating at 402.6 and 101.2 MHz, respectively. 31P{1H} NMR spectra were recorded on a Mercury 300 operating at 121.5 MHz. 29Si NMR spectra were recorded on a Varian Avance 600 operating at 119.203 MHz. GC analyses were carried out on a Varian CP-3800 (column: Rtx-5 30m I.D. 0.53 mm) equipped with TCD. Mass spectrometry analyses of ruthenium complexes were performed using Synapt G2-S mass spectrometer (Waters) equipped with the Electrospray ion source and quadrupole-time-of-flight mass analyzer. Isopropanol/acetonitrille mixture was used as a solvent. The D

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Organometallics

compound. Mass spectrometry analyses of monovinylgermasilsesqioxanes were performed using Synapt G2-S mass spectrometer (Waters) equipped with the ASAP (Atmospheric Solids Analysis Probe) ion source and quadrupole-time-of-flight mass analyzer. Small amounts of samples were applied directly onto the glass probe, and the excess of the sample was removed using a paper tissue. The measurements were performed in a gradient temperature rate from room temperature to 650 °C in 6 min with the desolvation gas flow 850 L/h and corona current set to 12 μA. Signals of the protonated ions of the compounds were present in the spectra, and some fragmentation related to ions generated in decomposition process was observed. The elemental compositions prediction for all the protonated ions confirmed their molecular formula and the isotopic profile. The chemicals were obtained from the following sources: dichloromethane, acetone, n-hexane, methanol, tetrahydrofuran, benzene-d6, toluene-d8, 2-methoxyethanol, triphenylphosphine, formaldehyde, copper(I) chloride, vinylmagnesium bromide, tributylchlorostannane, tetrachlorosilane, anthracene, calcium hydride, 1,1′-azobis(cyclohexanecarbonitrile, and anhydrous magnesium sulfate from Aldrich, triethylamine and silica gel 60 from Fluka, ruthenium(III) chloride hydrate from Lancaster, germanium tetrachloride from Merck, dichlorodimethylgermane from ABCR, trisilanolisobutyl POSS, trisilanoethyl POSS, trisilanolphenyl POSS, trisilanolcyclohexyl POSS, trisilanolcyclopentyl POSS from Hybrid Plastics and toluene from Chempur. Trichlorovinylgermane,13 [RuHCl(CO)(PPh3)3],15 monosilanolisobutyl POSS,16 and tributylvinylstannane17 were prepared according to the literature procedures. All solvents (except tetrahydrofuran) were dried prior to use over CaH2 and stored under argon. CH2Cl2 was additionally passed through a column with alumina, and after that it was degassed by repeated freeze−pump− thaw cycles. Tetrahydrofuran was dried over sodium benzophenone ketyl and freshly distilled prior to use. All reactions were carried out under a nitrogen atmosphere. 2. Synthesis of Chlorodimethylvinylgermane (6). A 100 mL high-pressure Rotaflo Schlenk vessel connected to gas and vacuum line was charged under argon with tributylvinylstannane (15 mL, 51.32 mmol), dichlorodimethylgermane (3.36 mL, 28.8 mmol) and 1,1′azobis(cyclohexanecarbonitrile) (1.76 g, 7.2 mmol). The whole mixture was frozen in liquid nitrogen bath and subjected to freeze− pump−thaw cycling. After the mixture was warmed to room temperature, it was heated on the oil bath for the 2 weeks at 150 °C. After the reaction was finished, the mixture was cooled to room temperature and transferred to a 50 mL round-bottom flask. Careful trap-to-trap distillation gave 3.6 g (75% yield) of chlorodimethylvinylgermane. 1 H NMR (C6D6, δ, ppm): 0.48 (s, 3H, CH3), 5.98 (m, 3H, −CH CH2); 13C{1H} NMR (CDCl3, δ, ppm): 3.00 (CH3), 132.50 (CH2), 137.00 (CH−Ge); MS: m/z (rel. intensity): 166 (1), 151 (100), 131 (20), 139 (22). Anal. Calcd (%) for C4H9ClGe: C, 29.08; H, 5.49. Found: C, 29.12; H, 5.56. 3. Synthesis of Vinylgermasilsesquioxanes. 3.1. Monovinylheptaethylgermasilsesquioxane (3a). A two-necked, 500 mL flask equipped with reflux condenser and connected to gas and vacuum line was charged under argon with trisilanolethyl POSS (5 g, 7.22 mmol), tetrahydrofuran (200 mL), and triethylamine (3.62 mL, 25.99 mmol). Then, vinyltrichlorogermane (1.08 mL, 8.66 mmol) was added dropwise to the mixture at room temperature, which resulted in the formation of a white precipitate. The suspension was stirred for 24 h at room temperature and filtered on a glass frit. After this time, tetrahydrofuran was evaporated from the filtrate on rotary evaporator and the residual solvent and triethylamine were removed under reduced pressure on the Schlenk line. Crude product was purified by precipitation in cold methanol−water solution and filtration. The product was thoroughly dried giving 3a as a white powder (isolated yield 92%). 1 H NMR (CDCl3, δ, ppm): 0.56−0.66 (m, 21H, CH3), 0.96−1.03 (m, 14H, CH2), 6.03 (dd, 1H, JHH = 19.9, 12.6 Hz, CHCH2), 6.14 (dd, 1H, JHH = 19.9, 3.1 Hz, CHCH2), 6.21 (dd, 1H, JHH = 12.6, 3.1 Hz, CHCH2); 13C{1H} NMR (CDCl3, δ, ppm): 4.12, 4.49 (CH2), 6.51, 6.73 (CH3), 126.39 (CH2), 137.23 (CH−Ge); 29Si NMR:

Scheme 9. Catalytic Coupling of (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane with Styrenesa

Conditions: toluene, 140 °C, closed high-pressure Schlenk flask,[5]: [H2CCH-C6H4-R] = 1:1.5, [RuHCl(CO)(PCy3)2] (1 mol %), 24 h; [a] not isolated; yield was determined by 1H NMR analysis.

a

Scheme 10. Homocoupling Reaction of (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane

measurement was performed in the positive ion mode with the desolvation gas flow 650 L/h and capillary voltage set to 4000 V with the flow rate 100 μL/min. The cations formed by the loss of the chloride anion and addition of the acetonitrile molecule were observed. The elemental compositions prediction for the ion confirmed the molecular formula and the isotopic profile of the E

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Scheme 11. Mechanism for the Formation of Ru−Ge Silsesquioxane Complexes and the Germylative Coupling of 5 with Styrene

(CDCl3, δ, ppm): −63.62, −65.11, −65.68; MS (ASAP): m/z (%): 660.96 (12), 662.96 (21), 664.96 (11), 678.97 (28), 682.98 (17), 689 (31), 691 (60), 693 (100), 694 (48), 695 (39), 701.98 (13), 702.98 (11), 703.99 (22), 704.98 (13); HRMS (ASAP) calcd for C16H39GeO12Si7, 693.0038; found, 693.0032. Anal. Calcd (%) for C16H38GeO12Si7: C, 27.78; H, 5.54. Found: C: 27.72; H: 5.50. 3.2. Monovinylheptaisobutylgermasilsesquioxane (3b). Substrate 3b was prepared using the same procedure and the following reagents: trisilanolisobutyl POSS (5 g, 6.32 mmol), triethylamine triethylamine (3.17 mL, 22.75 mmol) and vinyltrichlorogermane (0.95 mL, 7.58 mmol). Finally, a white precipitate was obtained (isolated yield = 89%). 1 H NMR (CDCl3, δ, ppm): 0.58−0.64 (m, 14H, CH2), 0.90−0.99 (m, 42H, CH3), 1.79−1.92 (m, 7H, CH), 6.01 (dd, 1H, JHH = 19.9, 12.6 Hz, CHCH2), 6.11 (dd, 1H, JHH = 19.9, 3.1 Hz, CHCH2), 6.19 (dd, 1H, JHH = 12.6, 3.1 Hz, CHCH2); 13C{1H} NMR (CDCl3, δ, ppm): 22.60, 22.92 (CH2), 23.86, 23.97 (CH), 25.68, 25.72 (CH3), 126.50 (CH2), 137.12 (CH−Ge); 29Si NMR: (CDCl3, δ, ppm): 65.68, −67.59, −68.11; MS (ASAP): m/z (%): 885.23 (40), 887.22 (68), 889.22 (100), 890.22 (66), 891.22 (54), 892.22 (28), 893.22 (13); HRMS (ASAP) calcd for C30H67GeO12Si7, 889.2229; found, 1889.2236. Anal. Calcd (%) for C30H66GeO12Si7: C, 40.57; H, 7.49. Found: C, 40.52; H, 7.43. 3.3. Monovinylheptaphenylgermasilsesquioxane (3c). Substrate 3c was prepared using the same procedure and the following reagents: trisilanolphenyl POSS (5 g, 4.86 mmol), triethylamine (2.44 mL, 17.51 mmol), and vinyltrichlorogermane (0.73 mL, 5.83 mmol). Finally, a white precipitate was obtained (isolated yield = 90%). 1 H NMR (CDCl3, δ, ppm): 6.16 (dd, 1H, JHH = 19.8, 12.3 Hz, CHCH2), 6.25 (dd, 1H, JHH = 17.1, 2.7 Hz, CHCH2), 6.30 (dd, 1H, JHH = 9.7, 2.7 Hz, CHCH2), 7.30−7.82 (m, 35H, Ph); 13C{1H} NMR (CDCl3, δ, ppm): 127.78 (CH2), 130.44, 130.52, 130.63, 131.19 (ipso-C of C6H5), 134.17 (CH−Ge); 29Si NMR: (CDCl3, δ, ppm): −76.96, −78.12, −78.58; MS (ASAP): m/z (%): 889.22 (25), 1025.01 (36), 1027.01 (62), 1029.01 (100), 1030.01 (72), 1031.01

(58), 1032.01 (30); HRMS (ASAP) calcd for C44H39GeO12Si7, 1029.0038; found, 1029.0056. Anal. Calcd (%) for C44H38GeO12Si7: C, 51.41; H, 3.73. Found: C, 51.37; H, 3.76. 3.4. Monovinylheptacyclopentylgermasilsesquioxane (3d). Substrate 3d was prepared using the same procedure and the following reagents: trisilanolcyclopentyl POSS (5 g, 5.14 mmol), triethylamine (2.60 mL, 18.50 mmol), and vinyltrichlorogermane (0.77 mL, 6.17 mmol). Finally, a white precipitate was obtained (isolated yield = 87%). 1 H NMR (CDCl3, δ, ppm): 0.88−1.14 (m, 7H, cyclopentyl−CH), 1.36−1.90 (m, 56H, cyclopentyl−CH2), 6.02 (dd, 1H, JHH = 19.8, 11.8 Hz, CHCH2), 6.12 (dd, 1H, JHH = 20.8, 5.0 Hz, CHCH2), 6.20 (dd, 1H, JHH = 8.4, 3.4 Hz, CHCH2); 13C{1H} NMR (CDCl3, δ, ppm): 22.34, 22.81 (cyclopentyl-CH), 26.97, 27.02, 27.30, 27.53 (cyclopentyl-CH2), 126.76 (CH2), 136.95 (CH−Ge); 29Si NMR: (CDCl3, δ, ppm): −64.26, −65.76, −66.35; MS (ASAP): m/z (%): 835.08 (49), 903.14 (17), 921.15 (100), 944.17 (76), 973.22 (80); HRMS (ASAP) calcd for C37H67GeO12Si7, 973.2209; found, 973.2229. Anal. Calcd (%) for C37H66GeO12Si7: C, 45.71; H, 6.84. Found: C, 45.68; H, 6.80. 3.5. Monovinylheptacyclohexylgermasilsesquioxane (3e). Substrate 3e was prepared using the same procedure and the following reagents: trisilanolcyclohexyl POSS (5 g, 4.67 mmol), triethylamine (2.34 mL, 16.82 mol), and vinyltrichlorogermane (0.7 mL, 5.6 mmol). Finally, a white precipitate was obtained (isolated yield = 84%). 1 H NMR (CDCl3, δ, ppm): 0.55−0.68 (m, 7H, cyclohexyl−CH), 0.99−1.19 (m, 35H, cyclohexyl−CH2), 1.47−1.68 (m, 35H, cyclohexyl−CH2), 5.87 (dd, 1H, JHH = 19.9, 12.9 Hz, CHCH2), 5.98 (dd, 1H, JHH = 19.9, 2.9 Hz, CHCH2), 6.06 (dd, 1H, JHH = 12.9, 2.8 Hz, CHCH2); 13C{1H} NMR (CDCl3, δ, ppm): 21.77, 22.74 (cyclohexyl-CH), 25.19, 25.42, 25.45, 26.05, 26.10 (cyclohexyl-CH2), 125.78 (CH2), 136.29 (CH−Ge); 29Si NMR: (CDCl3, δ, ppm): −68.56, −70.00, −70.52; MS (ASAP): m/z (%): 905.16 (39), 987.24 (15), 1005.25 (100), 1028.27 (72), 1071.33 (49); HRMS (ASAP) calcd for F

DOI: 10.1021/acs.organomet.5b00142 Organometallics XXXX, XXX, XXX−XXX

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Organometallics C44H81GeO12Si7, 1071.3319; found, 1071.3325. Anal. Calcd (%) for C44H80GeO12Si7: C, 49.37; H, 7.53. Found: C, 49.41; H, 7.49. 4. Synthesis of (Dimethylvinylgermoxy)heptaisobutylsilsesquioxane (5). A two-necked, 500 mL flask equipped with reflux condenser and connected to gas and vacuum line was charged under argon with monosilanolisobutyl POSS (1.5 g, 1.8 mmol), tetrahydrofuran (150 mL), and triethylamine (0.33 mL, 2.73 mmol). Then chlorodimethylvinylgermane (0.4 g, 2.42 mmol) was slowly added to the mixture at room temperature, which resulted in the formation of a white precipitate. The suspension was stirred for 24 h at room temperature and filtered on a glass frit. After this time, tetrahydrofuran was evaporated from the filtrate on rotary evaporator, and the residual solvent and triethylamine were removed under reduced pressure on the Schlenk line. Crude product was purified by precipitation in cold methanol−water solution and filtration. The product was thoroughly dried giving 6 as a white powder (isolated yield 85%). 1 H NMR (CDCl3, δ, ppm): 0.50 (s, 6H,-Ge(CH3)2-), 0.56−0.65 (m, 14H, CH2), 0.86−1.03 (m, 42H, CH3), 1.77−1.95 (m, 7H, CH), 5.75 (dd, 1H, JHH = 20.1, 2.9 Hz, CHCH2), 6.01 (dd, 1H, JHH = 13.7, 2.9 Hz, CHCH2), 6.32 (dd, 1H, JHH = 20.1, 13.7 Hz, CH CH2); 13C{1H} NMR (CDCl3, δ, ppm): 0.62 (-Ge(CH3)2-), 22.46, 22.53 (CH2), 23.80, 23.86 (CH), 25.68, 25.73 (CH3), 131.33 ( CH2), 138.31 (CH−Ge); 29Si NMR: (CDCl3, δ, ppm): −67.30, −67.90, −105.73; MS (ASAP): m/z (%):833.26 (57), 834.26 (40), 835.26 (29), 959.24 (34), 961.24 (68), 963.24 (100), 964.24 (69), 965.24 (57), 966.24 (30); HRMS (ASAP) calcd for C32H73GeO13Si8, 963.2417; found, 963.2432. Anal. Calcd (%) for C32H72GeO13Si8: C, 39.94; H, 7.54. Found: C, 39.89; H, 7.50. 5. Synthesis of Ruthenium−Germasilsesquioxane Complexes. 5.1. Synthesis of Complex (7a). A 50 mL high-pressure Schlenk vessel connected to gas and vacuum line was charged under argon with [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and dry toluene (20 mL). The mixture was warmed up in an oil bath to 110 °C and stirred for 15 min. Subsequently, monovinylheptaethylgermasilsesquioxane (0.145 g, 0.21 mmol) was added to the reacting mixture, and the suspension was refluxed for 24 h to give an orange solution. After this time, the solvent was evaporated under vacuum, and n-hexane (5 mL) was added to the remaining contents to form a yellow precipitate. Then, the resultant solution was decanted from precipitate, and the obtained solid was dried under vacuum (isolated yield = 89%). 1 H NMR (CDCl3, δ, ppm): 0.55−0.72 (m, 6H, CH3CH2-), 0.96 (dd, 8H, J = 16.2, 8.0 Hz, CH3CH2-), 1.10 (t, 9H, JHH = 7.6 Hz, CH3CH2-), 1.23−1.39 (m, 12H, CH3CH2-), 7.07−7.22 (m, 18H, Ph), 7.82−7.96 (m, 12H, Ph); 13C {1H} NMR (CDCl3, δ, ppm): 4.67, 5.04, 6.94, 7.01, 128.59 (t, J = 5.0 Hz), 128.71, 130.97, 132.10 (d, J = 2.5 Hz), 132.22, 132.30, 134.74 (t, J = 6.0 Hz); 29Si NMR: (CDCl3, δ, ppm): −65.64, −66.44, −68.42; 31P{1H} NMR: (CDCl3, δ, ppm): 38.68; IR (ν, cm−1): 1941.15 (CO); MS (ESI): 1355.08 (25), 1356.08 (49), 1357.08 (63), 1358.07 (94), 1359.07 (86), 1360.07 (100), 1361.08 (72), 1362.08 (61), 1363.08 (35); HRMS (ESI) calcd for C51H66ClGeO13P2RuSi7, 1360.0806; found, 1360.0751. Anal. Calcd (%) for C51H66ClGeO13P2RuSi7: C, 45.21; H, 4.91. Found: C, 45.21; H, 4.89. 5.2. Synthesis of Complex (7b). Complex 7b was prepared using the same procedure and the following reagents: [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and monovinylheptaisobutylgermasilsesquioxane (0.186 g, 0.21 mmol). Finally, a yellow precipitate was obtained (isolated yield = 85%). 1 H NMR (CDCl3, δ, ppm): 0.08 (d, 7H, J = 6.9 Hz, CH2), 0.57 (d, 7H, J = 7.0 Hz, CH2), 0.75 (d, 18H, J = 6.6 Hz, CH3), 0.96 (t, 24H, J = 7.8 Hz, CH3), 1.49−1.64 (m, 4H, CH), 1.79−1.96 (m, 3H, CH); 7.28−7.45 (m, 18H, Ph), 7.49−7.61 (m, 12H, Ph); 13C{1H} NMR (CDCl3, δ, ppm): 23.84−24.03 (CH2), 25.64−25.80 (CH), 25.89− 26.08 (CH3) 128.46, 128.56, 131.95 (d, J = 2.7 Hz), 132.07, 132.15, 132.97; 29Si NMR: (CDCl3, δ, ppm): −67.85, −68.67, −70.32; 31 1 P{ H} NMR: (CDCl3, δ, ppm): 37.70; IR (ν, cm−1): 1951.77 (CO); MS (ESI): m/z (%): 1551.30 (35), 1552.30 (49), 1553.30 (60), 1554.30 (97), 1555.30 (86), 1556.30 (100), 1557.30 (82), 1558.30 (70), 1559.30 (52), 1560.29 (29); HRMS (ESI) calcd for

C65H94ClGeO13P2RuSi7, 1556.2997; found, 1556.2979. Anal. Calcd (%) for C65H94ClGeO13P2RuSi7: C, 50.33; H, 6.11. Found: C, 50.27; H, 6.15. 5.3. Synthesis of Complex (7c). Complex 7c was prepared using the same procedure and the following reagents: [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and monovinylheptaphenylgermasilsesquioxane (0.22 g, 0.21 mmol). Finally, a yellow precipitate was obtained (isolated yield = 87%). 1 H NMR (CDCl3, δ, ppm): 6.50−7.86 (m, 65H, Ph); 13C{1H} NMR (CDCl3, δ, ppm): 127.45 (t, J = 4.9 Hz), 127.68, 127.77, 127.94, 128.37, 128.58, 128.68 (d, J = 3.8 Hz), 128.86, 130.33, 132.07 (d, J = 2.6 Hz), 132.20, 132.25, 133.79, 133.99, 134.14−134.81 (m); 29Si NMR: (CDCl3, δ, ppm): −77.26, −78.87, −82.05; 31P{1H} NMR: (CDCl3, δ, ppm): 39.50; IR (ν, cm−1): 1953.78 (CO); MS (ESI): m/z (%): 1693.09 (49), 1694.09 (78), 1695.09 (85), 1696.08 (100), 1697.08 (80), 1698.08 (76), 1699.09 (39); HRMS (ESI) calcd for C79H66ClGeO13P2RuSi7, 1696.0806; found, 1696.0844. Anal. Calcd (%) for C79H66ClGeO13P2RuSi7: C: 56.11, H: 3.93. Found: C: 55.09, H: 3.89. 5.4. Synthesis of Complex (7d). Complex 7d was prepared using the same procedure and the following reagents: [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and monovinylheptacyclopentylgermasilsesquioxane (0.204 g, 0.21 mmol). Finally, a yellow precipitate was obtained (isolated yield = 90%). 1 H NMR (CDCl3, δ, ppm): 0.84−1.05 (m, 7H, cyclopentyl-CH), 1.09−1.83 (m, 56H, cyclopentyl-CH2), 7.28−7.74 (m, 30H, Ph); 13 C{1H} NMR (CDCl3, δ, ppm): 22.85, 23.31, 23.38, 24.06, 24.07, 24.10, 25.86, 25.94, 26.08, 128.59 (t, J = 5.0 Hz), 128.70, 130.44, 130.88, 131.07, 131.23, 132.09 (d, J = 2.4 Hz), 132.22, 132.30, 134.79 (t, J = 5.9 Hz); 29Si NMR: (CDCl3, δ, ppm): −67.86, −68.67, −70.34; 31 1 P{ H} NMR: (CDCl3, δ, ppm): 38.48; IR (ν, cm−1): 1962.30 (CO); MS (ESI): 1419.23 (51), 1636.30 (54), 1637.29 (64), 1638.29 (82), 1639.30 (87), 1640.30 (100), 1641.30 (85), 1642.30 (67); HRMS (ESI) calcd for C72H94ClGeO13P2RuSi7, 1640.2997; found, 1640.2972. Anal. Calcd (%) for C72H94ClGeO13P2RuSi7: C: 52.88, H: 5.79. Found: C: 52.86, H: 5.77. 5.5. Synthesis of Complex (7e). Complex 7e was prepared using the same procedure and the following reagents: [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and monovinylheptacyclohexylgermasilsesquioxane (0.225 g, 0.21 mmol). Finally, a yellow precipitate was obtained (isolated yield =87%). 1 H NMR (CDCl3, δ, ppm): 0.68−1.87 (m 77H, C6H11), 7.28−7.42 (m, 18H, Ph), 7.50−7.61 (m, 12H, Ph); 13C{1H} NMR (CDCl3, δ, ppm): 23.55, 23.60, 23.97, 26.96 (d, J = 3.6 Hz), 27.08, 27.14, 27.20, 27.66, 27.78, 27.91, 128.56 (t, J = 5.0 Hz), 130.37, 130.46, 130.77, 131.08, 134.90 (t, J = 5.9 Hz); 29Si NMR: (CDCl3, δ, ppm): −68.34, −69.37, −71.34; 31P{1H} NMR: (CDCl3, δ, ppm): 40.06; IR (ν, cm−1): 1955.48 (CO); MS (ESI): 1732.41 (13), 1733.41 (26), 1734.41 (41), 1735.41 (57), 1736.41 (79), 1737.41 (85), 1738.41 (100), 1739.41 (84), 1740.41 (68), 1741.42 (45), 1742.41 (30), 1743.40 (14); HRMS (ESI) calcd for C79H108ClGeO13P2RuSi7, 1738.4093; found, 1738.4131. Anal. Calcd (%) for C79H108ClGeO13P2RuSi7: C, 54.74; H, 6.28. Found: C, 54.76; H, 6.30. 6. Synthesis of (Dimethylgermoxy)heptaisobutylsilsesquioxane Complex (8). Complex 8 was prepared using the same procedure and the following reagents: [RuHCl(CO)(PPh3)3] (0.2 g, 0.21 mmol) and (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.202 g, 0.21 mmol). Finally, a yellow precipitate was obtained (isolated yield = 85%). 1 H NMR (CDCl3, δ, ppm): 0.50 (s, 6H, -Ge(CH3)2-), 0.54−0.65 (m, 14H, CH2), 0.81−1.07 (m, 42H, CH3), 1.67−1.92 (m, 7H, CH), 7.28−7.74 (m, 30H, Ph); 13C{1H} NMR (CDCl3, δ, ppm): 13.39 (-Ge(CH3)2-) 22.28−22.60 (CH2), 23.68−23.90 (CH), 25.66−25.77 (CH3), 128.13 (t, J = 4.8 Hz), 128.46, 128.56, 131.94 (d, J = 2.7 Hz), 132.08, 132.15, 134.45, 134.60, 134.70 (t, J = 6.0 Hz); 29Si NMR: (CDCl3, δ, ppm): −66.73, −68.09, −110.00; 31P{1H} NMR: (CDCl3, δ, ppm): 35.10; IR (ν, cm−1): 1932.52 (CO); MS (ESI): 1624.32 (19), 1625.32 (29), 1626.32 (48), 1627.32 (58), 1628.32 (82), 1629.32 (88), 1630.32 (100), 1631.32 (82), 1632.32 (68), 1633.32 (50), G

DOI: 10.1021/acs.organomet.5b00142 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics

(m, 14H, CH2), 0.93−0.96 (m, 42H, CH3), 1.82−1.89 (m, 7H, CH), 6.63 (d, 1H, JHH = 18.9 Hz, CHGe), 6.95 (d, 1H, JHH = 18.9 Hz,  CH-C6H5), 7.19−7.45 (m, 5H, C6H5), 13C{1H} NMR (CDCl3, δ, ppm): 1.17 (-Ge(CH3)2-), 22.63, 22.69 (CH2), 23.97, 24.02 (CH), 25.84, 25.89 (CH3), 126.73, 127.95, 128.68, 131.50, 138.48 (CH− C6H5); 29Si NMR: (CDCl3, δ, ppm): −67.35, −67.99, −105.73 9b Isolated yield: 81%; 1H NMR (CDCl3, δ, ppm): 0.58 (s, 6H, -Ge(CH3)2-), 0.59−0.65 (m, 14H, CH2), 0.92−0.97 (m, 42H, CH3), 1.81−1.92 (m, 7H, CH), 6.59 (d, 1H, JHH = 19.1 Hz, CHGe), 6.89 (d, 1H, JHH = 19,1 Hz, CH-C6H4−Cl), 7.28−7.37 (m, 4H, C6H4Cl); 13C{1H} NMR (CDCl3, δ, ppm): 1.17 (-Ge(CH3)2-), 22.43− 22.72 (CH2), 23.95−24.01 (CH), 25.80−25.87 (CH3), 127.91, 128.88, 134.20, 136.12, 142.86 (CH−C6H4−Cl), 200.48 (CHGe); 29Si NMR: (CDCl3, δ, ppm): −67.27, −67.83, −101.00 9c Isolated yield: 85%; 1H NMR (CDCl3, δ, ppm): 0.50 (s, 6H, Ge(CH3)2-), 0.56−0.69 (m, 14H, CH2), 0.92−1.02 (m, 42H, CH3), 1.80−1.92 (m, 7H, CH), 3.82 (s, 3H, OCH3), 6.45 (d, 1H, JHH = 18.8 Hz, CHGe), 6.86 (d, 2H, JHH = 8.2 Hz, C6H4-OCH3), 6.88 (d, 1H, JHH = 19.2 Hz, CH-C6H4−OCH3), 7.37 (d, 2H, JHH = 8.8 Hz, C6H4OCH3); 13C{1H} NMR (CDCl3, δ, ppm): 1.17 (-Ge(CH3)2-), 22.63− 22.69 (CH2), 23.97−24.02 (CH), 25.84−25.89 (CH3), 31.08 (OCH3), 114.06, 128.02, 131.50, 138.48 (CH−C6H4−CF3), 207.08 ( CHGe); 29Si NMR: (CDCl3, δ, ppm): −67.31, −67.91, −105.74 9d Isolated yield: 87%; 1H NMR (CDCl3, δ, ppm): 0.58 (s, 6H, -Ge(CH3)2-), 0.58−0.60 (m, 14H, CH2), 0.93−0.96 (m, 42H, CH3), 1.83−1.87 (m, 7H, CH), 6.74 (d, 1H, JHH = 18.9 Hz, CHGe), 6.98 (d, 1H, JHH = 18.9 Hz, CH-C6H4−CF3), 7.52 (d, 2H, JHH = 7.9 Hz, C6H4-CF3), 7.58 (d, 2H, JHH = 7.9 Hz, C6H4-CF3); 13C{1H} NMR (CDCl3, δ, ppm): 1.18 (-Ge(CH3)2-), 22.44−22.81 (CH2), 23.95− 24.01 (CH), 25.81−25.86 (CH3), 125.70 (q, CF3), 126.87, 131.52, 140.93, 142.68(CH−C6H4−CF3); 29Si NMR: (CDCl3, δ, ppm): −67.27, −67.90, −108.14

1634.32 (31), 1635.31 (20); HRMS (ESI) calcd for C67H100ClGeO14P2RuSi8, 1630.3185; found, 1630.3219. Anal. Calcd (%) for C67H100ClGeO14P2RuSi8: C, 49.51; H, 6.20. Found: C, 49.48; H, 6.17. 7. Equimolar Reactions of Germanium−Silyl Complexes (7a) and (8) with Styrene. The stoichiometric reactions were performed in J-Young valve NMR tubes and controlled by 1H NMR spectroscopy. In a typical procedure, ruthenium complex 7a (0.015 g, 9.67 × 10−6 mol) and anthracene (0.0001g, internal standard) were dissolved in 0.65 mL of toluene-d8. Then the 1H NMR spectrum was recorded, and styrene (1.1 μL, 9.67 × 10−6 mol) was added under argon by microliter syringe. Then the reaction mixture was warmed up in an oil bath to 140 °C and heated for 24 h. After this time, the 1H NMR spectrum of the reaction mixture was taken. The equimolar reaction of ruthenium complex 8 with styrene was performed using the same procedure and the following reagents: ruthenium complex 12 (0.015 g, 9.23 × 10−6 mol), anthracene (0.0001g, internal standard), 0.65 mL of toluene-d8 and styrene (1.1 μL, 9.23 × 10−6 mol). 8. General Procedure for Catalytic Reactions. 8.1. Homocoupling of (5). A 10 mL high-pressure Schlenk vessel connected to gas and vacuum line was charged under argon with (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04 × 10−4 mol) and toluene (2 mL). The mixture was warmed up to 140 °C in an oil bath, and [RuHCl(CO)(PCy3)2] (0.0008 g, 1.04 × 10−6 mol) was added to the mixture under argon. The reaction mixture was heated in 140 °C for 24 h. Then the solvent was evaporated under vacuum and methanol (2 mL) was added to the residue to form a precipitate. The precipitate was filtered off and washed with methanol (2 × 2 mL) to remove ruthenium complexes. Reaction yield was calculated on the basis of the 1H NMR spectra of the reaction mixture. 8.2. Germylative Coupling of (5) with Styrenes. A 10 mL highpressure Schlenk vessel connected to gas and vacuum line was charged under argon with (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04 × 10−4 mol), toluene (2 mL), and olefin (1.56 × 10−4 mol). The mixture was warmed up to 140 °C in an oil bath and [RuHCl(CO)(PCy3)2] (0.0008 g, 1.04 × 10−6 mol) was added to the mixture under argon. The reaction mixture was heated in 140 °C for 24 h. Then the solvent was evaporated under vacuum and methanol (2 mL) was added to the residue to form a precipitate. The precipitate was filtered off and washed with methanol (2 × 2 mL) to remove ruthenium complexes. Reaction yield was calculated on the basis of the 1 H NMR spectra of the reaction mixture. 9. General Procedure for Synthesis of Functionalized (Dimethylstyrylgermoxy) Silsesquioxanes. 9.1. Via Homocoupling. A 10 mL high-pressure Schlenk vessel connected to gas and vacuum line was charged under argon with (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04 × 10−4 mol) and toluene (2 mL). The mixture was warmed up to 140 °C in an oil bath, and [RuHCl(CO)(PCy3)2] (0.0008 g, 1.04 × 10−6 mol) was added to the mixture under argon. The reaction mixture was heated in 140 °C for 24 h. Then the solvent was evaporated under vacuum and methanol (2 mL) was added to residue to form a precipitate. The precipitate was filtered off and washed with methanol (2 × 2 mL) to remove ruthenium complexes. Reaction yield was calculated on the basis of the 1 H NMR spectra of the reaction mixture. 9.2. Via Germylative Coupling with Styrenes. A 10 mL highpressure Schlenk vessel connected to gas and vacuum line was charged under argon with (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04 × 10−4 mol), toluene (2 mL), and olefin (1.56 × 10−4 mol). The mixture was warmed up to 140 °C in an oil bath, and [RuHCl(CO)(PCy3)2] (0.0008 g, 1.04 × 10−6 mol) was added to the mixture under argon. The reaction mixture was heated in 140 °C for 24 h. Then the solvent was evaporated under vacuum and methanol (2 mL) was added to residue to form a precipitate. The precipitate was filtered off and washed with methanol (2 × 2 mL) to remove ruthenium complexes. Reaction yield was calculated on the basis of the 1 H NMR spectra of the reaction mixture. 10. Analytical Data of Isolated Products. 9a Isolated yield: 88%; 1H NMR (CDCl3, δ, ppm): 0.59 (s, 6H,-Ge(CH3)2-), 0.59−0.65

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ASSOCIATED CONTENT

S Supporting Information *

Detailed X-ray analysis and crystal structure parameters are provided in the supporting materials. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.5b00142.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +48 (61) 8291987. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by a project of the National Science Centre (“Maestro”, UMO 2011/02/A/ST5/00472). REFERENCES

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DOI: 10.1021/acs.organomet.5b00142 Organometallics XXXX, XXX, XXX−XXX