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Supplementary Information

Visible light accelerated hydrosilylation of alkynes using platinum-[acyclic

diaminocarbene] photocatalysts

Jack C. Gee,[a] Beth A. Fuller,[a] Hannah-Marie Lockett,[a] Gita Sedghi,[a] Craig M. Robertson, and

Konstantin V. Luzyanin*[a,b]

aDepartment of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, United

Kingdom. E-mail: [email protected]

bSaint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg 199034, Russian

Federation.

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2018

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Contents

Materials and instrumentation

Synthesis and characterization of platinum-[acyclic diaminocarbene] species

Catalytic hydrosilylation of the terminal and internal alkynes

Optimization of the catalytic conditions

Labelling of the products derived from the hydrosilylation of the terminal alkynes

Labelling of the products derived from the hydrosilylation of the internal alkynes

Characterization of the hydrosilylation products

Hypothetic mechanism of the catalytic cycle

References

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Materials and instrumentation

Solvents, K2[PtCl4], xylyl isocyanide, 2-aminopyridine, and all reagents for catalytic studies were

obtained from commercial sources and used as received, apart from chloroform that was purified by

conventional distillation over calcium chloride. Complexes cis-[PtCl2(CNXyl)2],1 cis/trans-

[PtCl2(NCEt)2],2 cis-[PdCl2(NCMe)2],3 cis-[PdCl2(CNXyl)2],4 [Ir(ppy)2(µ-Cl)]2,5 and [IrHCl2(PPh3)3]6

were prepared as previously reported. C, H, and N elemental analyses were carried out by CHN-

Microanalytical Service of the University of Liverpool. HR-ESI+ mass-spectra were obtained on

MicroMass LCT and Agilent 6530B QTOF mass-spectrometers in MeOH or MeCN. MALDI-(TOF)-

MS spectra were acquired on Bruker Autoflex maX instrument using DCTB (trans-2-[3-(4-tert-

Butylphenyl)-2-methyl-2-propenylidene]malononitrile) matrix. Infrared spectra (4000–400 cm–1)

were measured on a Bruker Vertex-70 instrument in KBr pellets. 1D (1H, 13C{1H}) and 2D (1H,1H-

COSY, 1H,13C-HMQC/1H,13C-HSQC and 1H,13C-HMBC) NMR spectra were recorded on Bruker

Avance III HD 400 and 500 MHz (UltraShieldTM Plus Magnet) spectrometers at ambient temperature

using the solvent resonances as a reference.

X-ray Structure Determination. A single crystal of C42H41Cl5N6Pt2 (3) was selected and mounted on

a MiTeGen tip via crystallographic oil. Data were collected on a Mo Bruker APEX-II CCD

diffractometer. The crystal was kept at 100 K during data collection. Using Olex2,7 the structure was

solved with the ShelXT8 structure solution program using Intrinsic Phasing and refined with the

ShelXL9 refinement package using Least Squares minimisation. Supplementary crystallographic data

for this paper have been deposited at Cambridge Crystallographic Data Center (CCDC 1840742) and

can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.

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Synthesis and characterization of platinum-[acyclic diaminocarbene] species

Preparation of 2 via the reaction between cis-[PtCl2(CNXyl)2] (1) and 2-aminopyridine (Scheme

2, Route A). Solid 2-aminopyridine (0.25 mmol, 26.5 mg) was added to a solution of cis-

[PtCl2(CNXyl)2] (1, 0.25 mmol, 132.1 mg) in CHCl3 (10 mL). An immediate change of colour from

light to lemon yellow was observed, and the reaction mixture was then left to stand at 20–25 °C (RT)

for 12 h. After 12 h, the reaction mixture was filtered to remove a small amount of undissolved material

and evaporated to dryness at RT. Solid residue formed was washed with three 2 mL portions of Et2O

and then dried under vacuo at RT till constant weight. Yield of 2 was 85%, based on Pt.

[PtCl{C(NHC5H4N)–N(H)Xyl}(CNXyl)]Cl (2, 85% isolated yield). Anal.

Calcd for C23H24N4Cl2Pt: C 44.38; H 3.89; N 9.00. Found: C 44.28; H

3.80; N 9.08. HR-ESI+-MS (MeOH): found 587.1337 [M – Cl]+, calcd for

C23H24N4ClPt 587.1328; found 550.1563 [M – Cl – HCl]+, calcd for

C23H23N4Pt 550.1567. IR (KBr, selected bands, cm–1): ν(N–H) 3308 (m); ν(C–H) 2900 (m); ν(CºN)

2203 (s); ν(Ccarbene–N) and δ(N–H) 1550 (s) and 1629 (s); δ(C–H from aryls) 783 (s). 1H NMR (CDCl3,

298 K, 500.13 MHz, δ): 13.73 (s + d due to 3J(1H195Pt) 48 Hz, 1H, NH), 12.14 (s + d due to 3J(1H195Pt)

84 Hz, 1H, NH), 9.20 (d, 3J(1H1H) 5.9 Hz + d due to 3J(1H195Pt) 28 Hz, 1H, H1py), 8.02 (trd, 3J(1H1H)

5.9 Hz, 4J(1H1H) 1.5 Hz, 1H, H3py), 7.76–7.69 (m, br, 1H, H2

py), 7.45 (d, 3J(1H1H) 8.3 Hz, 1H, H4py),

7.20 (tr, 3J(1H1H) 7.6 Hz, 1H, p-Haryl from Xyl), 7.04 (d, 3J(1H1H) 7.6 Hz, 2H, m-Haryl from Xyl), 6.84

(d, 3J(1H1H) 7.7 Hz, 2H, m-Haryl from Xyl), 6.46 (tr, 3J(1H1H) 7.7 Hz, 1H, p-Haryl from Xyl), 2.45 (s)

and 2.23 (s, 12H, Me’s). 13C{1H} NMR (CDCl3, 298 K, 125.73 MHz, δ): 176.0 (Ccarbene–N), 158.9

(C5py), 145.9 (C1

py), 137.6 (C3py), 118.2 (C2

py), 114.2 (CºN), 111.0 (C4py), 143.6, 143.3, 136.0, 134.7,

130.2, 129.6, 128.5, 127.9 (C and CH from aryls), 19.2 and 18.5 (Me’s).

Complex 2 was characterized by elemental analyses (C, H, N), IR, high-resolution accurate-

mass ESI+-MS, and 1H and 13C{1H} NMR spectroscopy. Satisfactory C, H, and N elemental analyses

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was obtained for 2. HR-ESI+-MS for 2 showed peaks corresponding to the cation [M – Cl]+ and to the

[M – Cl – HCl]+ with the characteristic isotopic distribution. In the FT-IR spectra of 2, bands due to

ν(Ccarbene–N) and ν(N–H) appeared at 1550 cm–1 and 3308 cm–1, respectively. A strong ν(C≡N) stretch

due to the presence of the unreacted isocyanide ligand was found at ca. 2203 cm–1. Complex 2 shows

a single set of signals in the NMR spectra confirming its constant composition and structure. The 1H

NMR spectra of 2 displayed two well-resolved signals at 13.73 and 12.14 ppm assigned to the NH

from the carbene moiety; a characteristic feature of these two signals is the emergence of the satellites

due to coupling to the 195Pt nuclei via 3J(1H195Pt). In addition, a signal at 9.20 ppm, that was assigned

to the H1py, contains similar satellite structure due to coupling to the 195Pt nuclei via 3J(1H195Pt). All

these observations confirm the bidentate coordination mode of the carbene ligand, i.e. through the

carbene carbon and nitrogen of the pyridine moiety. In the 13C{1H} spectra, carbene signal resonate at

176.0 ppm, a typical value for the acyclic diaminocarbene ligands coordinated to platinum and

palladium centres. Gradient-enhanced 1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, and 1H,13C-

HMBC spectra aided the 1H and 13C signal assignment for the remaining signals in 2. All spectroscopic

and non-spectroscopic features of 2 match closely to those from the related palladium complexes

[PtCl{C(NHC5H4N)–N(H)R1}(CNR1)]Cl reported previously by some of us.10

Preparation of 3 via the reaction between cis-[PtCl2(CNXyl)2] (1) and 2 (Scheme 2, Route B). A

mixture of solid cis-[PtCl2(CNXyl)2] (1, 0.10 mmol, 52.8 mg) and 2 (0.10 mmol, 62.2 mg) was

dissolved in CHCl3 (10 mL). Solid K2CO3 (0.2 mmol, 27.6 mg) was then added and the reaction was

left to stand at 40 °C for 12 h under vigorous stirring. During the reaction time, the mixture turned

from pale yellow to lemon yellow. After 12 h, the reaction mixture was filtered to remove a small

amount of undissolved material and evaporated to dryness at RT. Solid residue formed was washed

with three 2 mL portions of Et2O and then dried under vacuo at RT till constant weight. Yield of 3 was

75%, based on Pt.

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3 (75% isolated yield). Anal. Calcd for C41H40N6Cl2Pt2: C 45.69; H

3.74; N 7.80. Found: C 45.82; H 3.66; N 7.82. HR- ESI+-MS

(MeOH): found 1078.2045 [M + H]+, calcd for C41H41N6Cl2Pt2

1078.2050; found 1041.2281 [M – Cl]+, calcd for C41H40N6ClPt2

1041.2282. IR (KBr, selected bands, cm–1): ν(C–H) 2987 (s), 2901

(s); ν(CºN) 2213 (s) and 2189 (s); ν(Ccarbene–N) 1633 (s), 1611 (s); δ(C–H from aryls) 747 (s). 1H

NMR (CDCl3, 298 K, 500.13 MHz, δ): 9.20 (dd, 3J(1H1H) 6.0 Hz, 4J(1H1H) 1.7 Hz, 1H, H1py), 9.17 (d,

3J(1H1H) 8.7 Hz, 1H, H4py), 7.87 (ddd, 3J(1H1H) 8.7 Hz, 3J(1H1H) 6.9 Hz 4J(1H1H) 1.7 Hz, 1H, H3

py),

7.18–7.16 (m, br, 1H, H2py), 7.11–7.04 (m, 4H, m+p-Haryl from Xyl), 6.94 (d, 3J(1H1H) 7.6 Hz, 2H, m-

Haryl from Xyl), 6.86 (d, 3J(1H1H) 7.7 Hz, 2H, m-Haryl from Xyl), 6.58 (d, 3J(1H1H) 7.6 Hz, 2H, m-Haryl

from Xyl), 6.41 (tr, 3J(1H1H) 7.6 Hz, 1H, p-Haryl from Xyl), 6.09 (tr, 3J(1H1H) 7.5 Hz, 1H, p-Haryl from

Xyl), 2.44 (s, 6H), 2.27 (s, 6H), 2.23(s, 6H), 2.06 (s, 6H, Me’s). 13C{1H} NMR (CDCl3, 298 K,

125.73 MHz, δ): 183.5 (Ccarbene–N) and 168.3 (Ccarbene–N), 152.6 (C5py), 145.3 (C1

py), 117.8 (C4py), ,

142.5 (C3py), 128.5 (C2

py), 142.0, 136.8, 136.2, 130.8, 128.8, 127.9, 127.7, 127.4, 126.9, 123.1 (C and

CH from aryls), 117.2 (CºN), 19.7, 19.3, 18.8 and 18.6 (Me’s).

Complex 3 was characterized by elemental analyses (C, H, N), IR, high-resolution accurate-

mass ESI+-MS, 1H and 13C{1H} NMR spectroscopy, and by the single crystal X-ray diffraction.

Satisfactory C, H, and N elemental analyses was obtained for 3. HR-ESI+-MS for 3 showed peaks

corresponding to the protonated molecular ion [M + H]+ as well as to the ion obtained due to the loss

of chloride ligand [M – Cl]+ with the characteristic isotopic distribution. In the FT-IR spectra of 3, two

bands due to ν(Ccarbene–N) appears at 1633 and 1611 cm–1, while two strong ν(C≡N) stretches due to

the presence of the unreacted isocyanide ligands were found at 2213 and 2189 cm–1. Complex 3 shows

a single set of signals in the NMR spectra confirming its constant composition and structure. The 1H

NMR spectra of 3 displayed signals at 9.20 (H1py), 9.17 (H4

py), 7.87 (H3py), and 7.18–7.16 (H2

py) ppm

with the characteristic pyridine type spin-spin system. In the 13C{1H} spectra, two carbene signals

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resonate at 183.5 and 168.3 ppm, that are typical values for the acyclic diaminocarbene ligands

coordinated to platinum and palladium centres.1, 10-11 Gradient-enhanced 1H,1H-COSY, 1H,13C-

HMQC/1H,13C-HSQC, and 1H,13C-HMBC spectra aided the 1H and 13C signal assignment for the

remaining signals in 3. All spectroscopic and non-spectroscopic features of 3 match closely to those

from the related binuclear palladium complexes reported previously by some of us.10, 12

The crystallographic data and processing parameters for 3 are summarized in Table S1, while

the corresponding plot can be found in Figure S1. Bond lengths and angles are given in Table S2 and

Table S3. In 3, both metal centres adopt a distorted square planar geometry with the isocyanide ligands

placed in the cis-position with respect to the carbon atom of each of the carbene ligands. In the first

aminocarbene species generated upon addition of 2-aminopyridine to 1, both C–N bonds are nearly

equal (C00G–N009 1.353(6), C00G–N00D 1.349(6)) and are intermediate between the typical double

and single bonds. That indicates a substantial delocalization of the electron density observed

commonly in the typical diaminocarbene structure.11f In the second aminocarbene moiety, generated

upon attack of 2 on the second molecule of 1, one bond is typical single (C00E–N00D 1.463(7)), while

the other is typical double (C00E–N00B 1.266(6)) indicating low degree of delocalization in it.

Structure of this carbene moiety is therefore closer to the amino(imino)carbene or carbene-like

structures reported previously for the products of the nucleophilic addition of imines to platinum- and

palladium-bound isocyanides.1, 13 Similar arrangements were previously observed for the

corresponding dinuclear palladium complexes, derived upon addition of 2-aminopyridine to

palladium-bound isocyanides.10 In the unreacted isocyanide ligands, the bond lengths of the CN groups

are 1.158(7) (for C00N–N00C) and 1.157(7) Å (for C00H–N00A), and are of typical values for the

CN triple bonds in platinum isocyanide complexes.14 Two Pt–C distances between each of the metal

centres and the respective aminocarbene ligands (1.974(5) for Pt01–C00G and 1.974(6) for Pt02–

C00E) are nearly similar; the same is valid for both Pt–C distances between metal centres and

corresponding isocyanide ligands (1.913(6) for Pt01–C00N, 1.912(6) for Pt02–C00H). The fused

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metallacycles formed upon generation of 3 via the addition of 2 to 1, are roughly planar, and the angles

around both platinum centres are identical (79.0(2)). All other bond lengths and angles in 3 are of

normal values for platinum-isocyanide and diaminocarbene complexes reported previously.1, 15

Figure S1. View of 3 with the atomic numbering scheme. Thermal ellipsoids are drawn with 50%

probability. Hydrogen labels are omitted for simplicity.

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Table S1. Crystal data and structure refinement for 3 Identification code 3 Empirical formula C42H41Cl5N6Pt2 Formula weight 1197.24 Temperature/K 100 Crystal system triclinic Space group P-1 a/Å 10.8699(6) b/Å 12.8241(8) c/Å 17.0041(10) α/° 109.7880(10) β/° 96.4340(10) γ/° 99.5290(10) Volume/Å3 2163.2(2) Z 2 ρcalcg/cm3 1.838 µ/mm-1 6.806 F(000) 1152.0 Crystal size/mm3 0.6 × 0.2 × 0.2 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/° 2.588 to 52.956 Index ranges -13 ≤ h ≤ 13, -16 ≤ k ≤ 16, -21 ≤ l ≤ 21 Reflections collected 32975 Independent reflections 8883 [Rint = 0.0609, Rsigma = 0.0638] Data/restraints/parameters 8883/0/504 Goodness-of-fit on F2 1.008 Final R indexes [I>=2σ (I)] R1 = 0.0332, wR2 = 0.0574 Final R indexes [all data] R1 = 0.0542, wR2 = 0.0643 Largest diff. peak/hole / e Å-3 1.17/-0.99

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Table S2. Bond lengths for 3 Atom Atom Length/Å Atom Atom Length/Å Pt01 Cl03 2.3549(14) C00L C00O 1.393(8) Pt01 N008 2.030(4) C00L C00T 1.374(8) Pt01 C00G 1.974(5) C00M C016 1.490(8) Pt01 C00N 1.913(6) C00M C01G 1.392(8) Pt02 Cl04 2.4083(13) C00O C00P 1.393(7) Pt02 N009 2.059(4) C00O C011 1.492(8) Pt02 C00E 1.974(6) C00P C00Z 1.404(8) Pt02 C00H 1.912(6) C00Q C00R 1.490(8) Cl05 C013 1.760(6) C00R C00X 1.398(7) Cl06 C013 1.760(6) C00R C01D 1.394(7) Cl07 C013 1.775(6) C00S C014 1.388(8) N008 C00J 1.356(7) C00S C017 1.506(8) N008 C00Y 1.350(6) C00T C019 1.383(8) N009 C00G 1.353(6) C00U C015 1.505(7) N009 C00J 1.393(6) C00V C014 1.388(9) N00A C00H 1.157(7) C00V C01G 1.360(9) N00A C01I 1.407(7) C00W C018 1.384(7) N00B C00E 1.266(6) C00X C01E 1.403(8) N00B C00X 1.411(7) C00Y C018 1.376(7) N00C C00N 1.158(7) C00Z C010 1.498(8) N00C C00P 1.409(7) C00Z C019 1.386(8) N00D C00E 1.463(7) C012 C01E 1.505(7) N00D C00G 1.349(6) C015 C01I 1.400(8) N00D C00I 1.452(6) C01A C01B 1.371(8) C00F C00J 1.379(7) C01A C01F 1.508(8) C00F C00W 1.393(7) C01A C01I 1.402(7) C00I C00M 1.397(7) C01B C01C 1.389(8) C00I C00S 1.396(7) C01D C01J 1.375(8) C00K C015 1.386(7) C01E C01H 1.391(8) C00K C01C 1.372(8) C01H C01J 1.396(8)

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Table S3. Bond angles for 3 Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚ N008 Pt01 Cl03 93.80(13) C00L C00O C011 122.8(5) C00G Pt01 Cl03 172.71(16) C00P C00O C011 122.0(5) C00G Pt01 N008 79.0(2) C00O C00P N00C 117.2(5) C00N Pt01 Cl03 85.40(17) C00O C00P C00Z 125.2(5) C00N Pt01 N008 177.8(2) C00Z C00P N00C 117.6(5) C00N Pt01 C00G 101.8(2) C00X C00R C00Q 121.9(5) N009 Pt02 Cl04 100.57(12) C01D C00R C00Q 119.9(5) C00E Pt02 Cl04 175.97(16) C01D C00R C00X 118.1(5) C00E Pt02 N009 79.0(2) C00I C00S C017 121.5(5) C00H Pt02 Cl04 83.28(17) C014 C00S C00I 117.3(5) C00H Pt02 N009 175.90(19) C014 C00S C017 121.1(5) C00H Pt02 C00E 97.1(2) C00L C00T C019 120.3(6) C00J N008 Pt01 113.9(3) C01G C00V C014 120.6(6) C00Y N008 Pt01 126.1(4) C018 C00W C00F 119.6(5) C00Y N008 C00J 119.6(5) C00R C00X N00B 121.1(5) C00G N009 Pt02 115.1(3) C00R C00X C01E 121.8(5) C00G N009 C00J 114.8(4) C01E C00X N00B 116.7(5) C00J N009 Pt02 129.9(4) N008 C00Y C018 121.9(5) C00H N00A C01I 172.2(6) C00P C00Z C010 121.2(5) C00E N00B C00X 123.6(5) C019 C00Z C00P 115.9(5) C00N N00C C00P 174.5(5) C019 C00Z C010 122.8(6) C00G N00D C00E 117.8(4) Cl05 C013 Cl06 110.5(3) C00G N00D C00I 124.9(4) Cl05 C013 Cl07 109.0(3) C00I N00D C00E 117.3(4) Cl06 C013 Cl07 110.0(4) N00B C00E Pt02 135.9(4) C00V C014 C00S 120.6(6) N00B C00E N00D 113.1(5) C00K C015 C00U 121.9(5) N00D C00E Pt02 111.0(3) C00K C015 C01I 115.3(5) C00J C00F C00W 119.2(5) C01I C015 C00U 122.8(5) N009 C00G Pt01 116.2(4) C00Y C018 C00W 118.7(5) N00D C00G Pt01 130.6(4) C00T C019 C00Z 121.3(6) N00D C00G N009 113.3(5) C01B C01A C01F 123.3(5) N00A C00H Pt02 174.3(5) C01B C01A C01I 116.7(5) C00M C00I N00D 117.5(5) C01I C01A C01F 120.0(5) C00S C00I N00D 119.3(5) C01A C01B C01C 121.5(6) C00S C00I C00M 123.1(5) C00K C01C C01B 119.6(6) N008 C00J N009 115.2(5) C01J C01D C00R 120.8(5) N008 C00J C00F 120.8(5) C00X C01E C012 120.2(5) C00F C00J N009 123.9(5) C01H C01E C00X 118.5(5)

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C01C C00K C015 122.7(6) C01H C01E C012 121.3(5) C00T C00L C00O 122.2(6) C00V C01G C00M 121.6(6) C00I C00M C016 120.6(5) C01E C01H C01J 120.0(6) C01G C00M C00I 116.8(6) C015 C01I N00A 118.2(5) C01G C00M C016 122.7(5) C015 C01I C01A 124.2(5) N00C C00N Pt01 170.5(5) C01A C01I N00A 117.6(5) C00L C00O C00P 115.1(6) C01D C01J C01H 120.7(6)

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Photophysical measurements

To understand whether complexes [2] and [3] absorb light, UV-vis measurements were undertaken

(Figure S2). Both diaminocarbene species prepared are noticeably yellow, and they absorb light

below 450 nm as shown in Figure S2; absorption is extended to the UV region down to ca. 350 nm.

Complexes [2] and [3] are not fluorescent and/or phosphorescent, and no emission bands were

detected. Model hydrosilylation substrates do not absorb in this region.

Figure S2. UV-vis spectra of [2] (2.5´10–3 M), [3] (2.5´10–3 M), diphenylacetylene (2.5´10–1 M),

and triethylsilane (2.5´10–1 M) in toluene.

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Taking these results into account we looked for a suitable light source and focused our attention

on blue LED H150B from Kessil (36 W) that produces an emission spectrum in the 400–500 nm range

with two maxima at ca. 420 and 440 nm, that is within the absorption region for [2] and [3].

Additional UV-vis studies showed that the absorption spectra of the solution of [2] or [3] in

toluene do not change upon irradiation at RT (alone and/or in the presence of substrates/additives).

Irradiation of the solution of catalysts in toluene at 40–60 °C (model catalytic conditions) without any

substrates added rendered the UV-vis spectra without any visible changes.

Figure S3. UV-vis spectra of the model catalytic mixture containing catalysts [2] (2.5´10–3 M) or [3]

(2.5´10–3 M), diphenylacetylene (2.5´10–1 M), and triethylsilane (2.5´10–1 M) in toluene before and

after the catalytic run at 60 °C for 12 h.

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Figure S3 shows the UV-vis absorbance spectra of the same catalytic system containing [2]

or [3] (2.5´10–3 M), diphenylacetylene (2.5´10–1 M), and triethylsilane (2.5´10–1 M) in toluene before

and after the catalytic run. After the catalytic run, a decrease of the absorbance of solution in the region

400–450 nm is evident, presumably due to transformation of [2] or [3] into other species, for instance

during pre-catalyst activation step. Some absorption is however retained (Figure S3). No any emission

bands were evident in the emission spectra upon completion of the catalytic runs even upon a broad

variation of ratio of substrates, catalyst concentration, temperature and time.

Quantum yield estimation. Estimate of quantum yield was done using similar approach described

previously for photocatalytic radical hydrosilylation of alkynes.16 Thus, a toluene solution of a model

catalytic reaction, containing diphenylacetylene (2.5´10–3 M), triethylsilane (2.5´10–3 M), and catalyst

[2] or [3] (2.5´10–3 M), was irradiated using Kessil KSH150B34 blue LED lamp (Phn = 60 mW*cm–

2, Shn = 5 cm2) at 60 °C for 1 h. Corresponding product was formed in 28% yield for catalyst [2] or

32% for catalyst [3] (NMR yield using 1,4-dimethoxybenzene as an internal standard). Light intensity

was determined with the help of the Thorlabs PM100D power meter console equipped with the S320C

thermal power head. All calculations were done as described in Ref. 16, giving an apparent quantum

yield (Fapparent) at l = 420 nm of 0.185 for the reaction with catalyst [2] and 0.211 for [3]. Internal

quantum yield (Finternal) considering actual absorbance of the reaction mixture (A for [2] 0.22, A for

[3] 0.24) was 0.466 for reaction with catalyst [2] and 0.495 for [3].

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Catalytic hydrosilylation of the terminal and internal alkenes

General procedure for the catalytic hydrosilylation of the terminal and internal alkynes using

platinum-[ADC]s as photocatalyst. Alkyne (5.0×10–4 mol), silane (5.0×10–4 mol), slected catalyst

(5.0×10–7 mol), toluene (2.0 mL), and a PTFE-coated magnetic bar were placed in a 5-mL vial. The

vial was closed with a septum, sealed with an aluminium crimp seal with an open top, and vented using

a needle through several cycles of vacuum/dinitrogen flow. For the experiments under visible light

irradiation, 34 W Blue LED lamp (Kessil KSH150B) was placed at the distance of 10 cm of the centre

of the reaction vial, and the vials were kept at 40–60 °C in the oil bath for 12–24 h (see Tables 1–3 for

details). For the experiments without visible light irradiation, each vial was covered with 2 layers of

the aluminium foil and no lamp was used. After completion of the reaction time, catalytic mixtures

were cooled down to RT, evaporated to dryness under a stream of dinitrogen, and the content of the

vial was extracted with three 0.20 mL portions of CDCl3. All fractions were joined followed by the

addition of 1,2-dimethoxyethane or 1,4-dimethoxybenzene (1 equiv, used as an NMR internal

standard), and then analysed by 1H NMR spectroscopy. The isomeric content was determined based

on the alkene coupling constants in the 1H NMR spectra and/or analysis of chemical shifts, while

quantifications were performed upon integration of the selected peaks of the product against peaks of

1,2-dimethoxyethane. Vinyl silane products were not isolated individually but characterized in the

reaction mixture using 1H NMR spectroscopy; full peaks assignment was done using multiplet fine

structure analysis and/or data from additional 1H,1H-COSY and 1H,13C-HSQC experiments (when

required). All the spectral data obtained were matched to those available from previous reports.

S17

Optimisation of the catalytic conditions

Table S4. Optimization of the catalytic conditions in the model hydrosilylation system with and

without visible light irradiation.a

Entry Catalyst Product yield with light ON

Product yield with light OFF

Reactions at 20 ºC for 48 h

A1–2 No catalyst added <5 <5

A3–4 cis/trans-[PtCl2(NCEt)2] <5 <5

A5–6 cis-[PtCl2(CNXyl)2] (1) <5 <5

A7–8 Catalyst [2] 6 <5

A9–10 Catalyst [3] 6 <5

A11–12 Catalyst [2] <5b <5

A13–14 Catalyst [3] <5b <5

A15–16 cis-[PdCl2(NCMe)2] <5 <5

A17–18 cis-[PdCl2(CNXyl)2] <5 <5

A19–20 [Ir(ppy)2(µ-Cl)]2 <5 <5

A21–22 [IrHCl2(PPh3)3] <5 <5


B1–2 No catalyst added <5 <5

B3–4 cis/trans-[PtCl2(NCEt)2] <5 <5

B5–6 cis-[PtCl2(CNXyl)2] (1) 8 <5

B7–8 Catalyst [2] 24 <5

B9–10 Catalyst [3] 32 <5

B11–12 Catalyst [2] 14b <5

B13–14 Catalyst [3] 16b <5

B15–16 cis-[PdCl2(NCMe)2] <5 <5

B17–18 cis-[PdCl2(CNXyl)2] <5 <5

Ph HSiEt3H

PhPh

Et3Si

cat. 0.1 mol%

Ph

S18

B19–20 [Ir(ppy)2(µ-Cl)]2 8 <5

B21–22 [IrHCl2(PPh3)3] <5 <5


C1–2 No catalyst added <5 <5

C3–4 cis/trans-[PtCl2(NCEt)2] <5 <5

C5–6 cis-[PtCl2(CNXyl)2] (1) 12 <5

C7–8 Catalyst [2] 78 8

C9–10 Catalyst [3] 87 12

C11–12 Catalyst [3] 89c 14

C13–14 Catalyst [2] 14b 8

C15–16 Catalyst [3] 16b 12

C17–18 Catalyst [2] 16d <5

C19–20 Catalyst [3] 23d <5

C21–22 cis-[PdCl2(NCMe)2] <5 <5

C23–24 cis-[PdCl2(CNXyl)2] <5 <5

C25–26 [Ir(ppy)2(µ-Cl)]2 10 <5

C27–28 [IrHCl2(PPh3)3] <5 <5

PhC≡CPh (5.0´10–4 mol, 1 equiv), Et3SiH (5.0´10–4 mol, 1 equiv), selected catalyst (5.0´10–7 mol); toluene (2.0 mL); 34 W blue LED used for experiments under visible light irradiation. aYields of product were determined with the help of 1H NMR spectroscopy using 1,2-dimethoxyethane as a standard. bIrradiation with 34 W blue LED source for 1h only, then the reaction was allowed to continue in the darkness. cCatalyst loading 1 mol%, reaction time 4 h. dCatalyst loading 0.01 mol%, reaction time 24 h.

S19

Table S5. Labelling of the products derived from the hydrosilylation of the terminal alkynes.

Entry Substrates PhCºCH 4-(t-Bu)C6H4CºCH t-BuCºCH

1–3 Et3SiH VS1a(b-E)/ VS1b(a)

VS2a(b-E)/ VS2b(a)

VS3a(b-E)/ VS3b(a)

4–6 Pr3SiH VS4a(b-E)/ VS4b(a)

VS5a(b-E)/ VS5b(a)

VS6a(b-E)/ VS6b(a)

7–9 i-Pr3SiH VS7a(b-E)/

VS7b(a) VS8a(b-E)/

VS8b(a) VS9a(b-E)/

VS9b(a)

10–12 PhMe2SiH VS10a(b-E)/ VS10b(a)

VS11a(b-E)/ VS11b(a)

VS12a(b-E)/ VS12b(a)

Table S6. Labelling of the products derived from the hydrosilylation of the internal alkynes

Entry Alkyne Silane Product

1 PhCºCPh Et3SiH VS13

2 PhCºCPh PhMe2SiH VS14

3 Me(CH2)2CºC(CH2)2Me Et3SiH VS15

4 Me(CH2)2CºC(CH2)2Me PhMe2SiH VS16

5 PhCºCMe Et3SiH VS17a / VS17b

6 PhCºCMe PhMe2SiH VS18a / VS18b

S20

Characterization of the hydrosilylation products

(E)-(Styryl)triethylsilane (VS1a).17 Prepared: 1H NMR (400.13 MHz, CDCl3): d =

7.45 (d, J 8.2 Hz, 2H, CH-aryls), 7.34 (t, J 7.7 Hz, 2H, CH-aryls), 7.25 (m, 1H,

CH-aryl), 6.91 (d, J 19.2 Hz, 1H, C=CH), 6.44 (d, J 19.2 Hz, 1H, C=CH), 1.00 (t,

J 8.0 Hz, 9H, CH2Me), 0.68 (q, J 8.0 Hz, 6H, CH2Me). From Ref. 17d: 1H NMR (600 MHz, CDCl3): d

= 7.36–7.00 (m, 5H, CH-aryls), 6.80 (d, J 19.7 Hz, 1H, C=CH), 6.35 (d, J 19.7 Hz, 1H, C=CH), 0.91

(t, J 8.0 Hz, 9H, CH2Me), 0.58 (q, J 8.0 Hz, 6H, CH2Me).

(1-Phenylvinyl)triethylsilane (VS1b).17a, 17b, 17d, 18 Prepared: 1H NMR (400.13 MHz,

CDCl3): d = 7.7–7.2 (m, 5H, CH-aryls), 5.88 (d, J 2.8 Hz, 1H, C=CH2), 5.59 (d, J 2.8

Hz, 1H, C=CH2), 0.94 (t, J 8.0 Hz, 9H, CH2Me), 0.58 (q, J 8.0 Hz, 6H, CH2Me).

From Ref. 17d: 1H NMR (600 MHz, CDCl3): d = 7.35–7.01 (m, 5H, CH-aryls), 5.77 (d, J 2.9 Hz, 1H,

C=CH2), 5.47 (d, J 2.9 Hz, 1H, C=CH2), 0.85 (t, J 8.0 Hz, 9H, CH2Me), 0.53 (q, J 8.0 Hz, 6H, CH2Me).

(E)-(4-(tert-Butyl)styryl)triethylsilane (VS2a).17a Prepared: 1H NMR (400

MHz, CDCl3): d = 7.7–7.2 (m, 4H, CH-aryls), 6.89 (d, J 19.2 Hz, 1H, C=CH),

6.38 (d, J 19.2 Hz, 1H, C=CH), 1.32 (s, 9H, CMe3), 0.98 (t, J 7.9 Hz, 9H,

CH2Me), 0.65 (q, J 7.9 Hz, 6H, CH2Me). From Ref. 17a: 1H NMR (300 MHz,

CDCl3): d = 7.38 (m, 4H, CH-aryls), 6.89 (d, J 19.2 Hz, 1H, C=CH), 6.38 (d, J 19.2 Hz, 1H, C=CH),

1.32 (s, 9H, CMe3), 0.99 (t, J 8.0 Hz, 9H, CH2Me), 0.66 (q, J 8.0 Hz, 6H, CH2Me).

(1-(4-(tert-Butyl)phenyl)vinyl)triethylsilane (VS2b).17a, 18. Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.6–7.2 (m, 4H, CH-aryls), 5.91 (d, J 2.7 Hz, 1H,

C=CH), 5.55 (d, J 2.7 Hz, 1H, C=CH), 1.30 (s, 9H, CMe3), 1.01 (t, J 7.9 Hz, 9H,

CH2Me), 0.69 (q, J 7.9 Hz, 6H, CH2Me). From Ref. 17a, 18: 1H NMR (300 MHz,

CDCl3): d = 7.7–7.2 (m, 4H, CH-aryls), 5.90 (d, J 2.8 Hz, 1H, C=CH), 5.55 (d, J 2.8 Hz, 1H, C=CH),


S21

(E)-(3,3-Dimethylbut-1-en-1-yl)triethylsilane (VS3a).17b, 19 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 6.02 (d, J 19.2 Hz, 1H, C=CH), 5.42 (d, J 19.2 Hz, 1H,

C=CH), 1.00 (s, 9H, CMe3), 0.93 (t, J 7.8 Hz, 9H, CH2Me), 0.56 (q, J 7.8 Hz, 6H, CH2Me). From Ref.

19a: 1H NMR (400 MHz, CDCl3): d = 6.04 (d, J 19.2 Hz, 1H, C=CH), 5.42 (d, J 19.2 Hz, 1H, C=CH),


(3,3-Dimethylbut-1-en-2-yl)triethylsilane (VS3b).17b Prepared: 1H NMR (400.13

MHz, CDCl3): d = 5.75 (d, J 2.0 Hz, 1H, C=CH), 5.30 (d, J 2.0 Hz, 1H, C=CH), 0.99

(s, 9H, CMe3), 0.90 (t, J 7.8 Hz, 9H, CH2Me), 0.52 (q, J 7.8 Hz, 6H, CH2Me). From Ref. 17b: 1H NMR

(250 MHz, CDCl3): d = 5.75 (d, J 1.98 Hz, 1H, C=CH), 5.29 (d, J 1.98 Hz, 1H, C=CH), 1.00 (s, 9H,

CMe3), 0.92 (t, 9H, CH2Me), 0.54 (q, 6H, CH2Me).

(E)-(Styryl)tripropylsilane (VS4a).18 Prepared: 1H NMR (400.13 MHz, CDCl3): d

= 7.46 (d, J 7.6 Hz, 2H, CH-aryls), 7.4–7.2 (m, 1H, CH-aryl), 7.19 (d, J 7.6 Hz,

2H, CH-aryls), 6.88 (d, J 19.3 Hz, 1H, C=CH), 6.44 (d, J 19.3 Hz, 1H, C=CH),

1.01 (t, 9H, J 7.8 Hz, SiCH2CH2CH3), 0.95 (t, J 7.8 Hz, 6H, SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H,

SiCH2CH2CH3). From Ref. 18: 1H NMR (300 MHz, CDCl3): d = 7.45 (d, J 7.8 Hz, 2H, CH-aryls),

7.35–7.19 (m, 2H, CH-aryls), 7.16–7.14 (m, 1H, CH-aryl), 6.90 (d, J 19.3 Hz, 1H, C=CH), 6.43 (d, J

19.3 Hz, 1H, C=CH), 0.99 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J 7.9 Hz, 6H, SiCH2CH2CH3),

0.66 (q, J 7.8 Hz, 6H, SiCH2CH2CH3).

(1-Phenylvinyl)tripropylsilane (VS4b).18 Prepared: 1H NMR (400.13 MHz, CDCl3):

d = 7.45 (d, J 7.8 Hz, 2H, CH-aryl), 7.4–7.2 (m, 2H, CH-aryls), 7.2–7.1 (m, 1H, CH-

aryl), 5.85 (d, J 3.1 Hz, 1H, C=CH2), 5.57 (d, J 3.1 Hz, 1H, C=CH2), 0.99 (t, 9H, J 7.9

Hz, SiCH2CH2CH3), 0.93 (t, J 7.9 Hz, 6H, SiCH2CH2CH3), 0.66 (q, J 7.8 Hz, 6H, SiCH2CH2CH3).

From Ref. 18: 1H NMR (300 MHz, CDCl3): d = 7.45 (d, J 7.8 Hz, 2H, CH-aryl), 7.35–7.19 (m, 2H,

CH-aryl), 7.16–7.14 (m, 1H, CH-aryl), 5.87 (d, J 3.1 Hz, 1H, C=CH2), 5.57 (d, J 3.1 Hz, 1H, C=CH2),

S22

0.99 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J 7.9 Hz, 6H, SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H,

SiCH2CH2CH3).

(E)-(4-(tert-Butyl)styryl)tripropylsilane (VS5a).18 Prepared: 1H NMR (400.13

MHz, CDCl3): d = 7.39 (d, J 8.2 Hz, 2H, CH-aryls), 7.36 (d, J 8.2 Hz, 2H, CH-

aryls), 6.88 (d, J 19.2 Hz, 1H, C=CH), 6.41 (d, J 19.2 Hz, 1H, C=CH), 1.33 (s,

9H, CMe3), 0.99 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J 7.9 Hz, 6H,

SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H, SiCH2CH2CH3). From Ref. 18: 1H NMR (300 MHz, CDCl3): d

= 7.39 (d, J 8.2 Hz, 2H, CH-aryls), 7.36 (d, J 8.2 Hz, 2H, CH-aryls), 6.88 (d, J 19.2 Hz, 1H, C=CH),

6.41 (d, J 19.2 Hz, 1H, C=CH), 1.33 (s, 9H, CMe3), 0.99 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J

7.9 Hz, 6H, SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H, SiCH2CH2CH3).

(1-(4-(tert-Butyl)phenyl)vinyl)tripropylsilane (VS5b).18 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.33 (d, J 8.2 Hz, 2H, CH-aryls), 7.11 (d, J 8.2 Hz, 2H,

CH-aryls), 5.88 (d, J 3.2 Hz, 1H, C=CH), 5.56 (d, J 3.2 Hz, 1H, C=CH), 1.33 (s,

9H, CMe3), 1.01 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J 7.9 Hz, 6H,

SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H, SiCH2CH2CH3). From Ref. 18: 1H NMR (300 MHz, CDCl3): d

= 7.33 (d, J 8.2 Hz, 2H, CH-aryls), 7.11 (d, J 8.2 Hz, 2H, CH-aryls), 5.88 (d, J 3.1 Hz, 1H, C=CH),

5.55 (d, J 3.1 Hz, 1H, C=CH), 1.33 (s, 9H, CMe3), 0.99 (t, 9H, J 7.9 Hz, SiCH2CH2CH3), 0.93 (t, J 7.9

Hz, 6H, SiCH2CH2CH3), 0.67 (q, J 7.8 Hz, 6H, SiCH2CH2CH3).

(E)-(3,3-Dimethylbut-1-en-1-yl)tripropylsilane (VS6a).18 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 6.04 (d, J 18.8 Hz, 1H, C=CH), 5.47 (d, J 18.8 Hz, 1H,

C=CH), 1.45–1.30 (m, 9H, CH2CH2Me), 0.99 (s, 9H, CMe3), 0.95 (t, J 7.4 Hz, 9H, CH2CH2Me), 0.60–

0.54 (q, J 7.6 Hz, 6H, CH2CH2Me). From Ref. 18: 1H NMR (300 MHz, CDCl3): d = 6.01 (d, J 19.1 Hz,

1H, C=CH), 5.45 (d, J 19.1 Hz, 1H, C=CH), 1.44–1.27 (m, 9H, CH2CH2Me), 0.98 (s, 9H, CMe3), 0.95

(t, J 7.2 Hz, 9H, CH2CH2Me), 0.59–0.53 (q, J 7.8 Hz, 6H, CH2CH2Me).

S23

(3,3-Dimethylbut-1-en-2-yl)tripropylsilane (VS6b).18 Prepared: 1H NMR (400.13

MHz, CDCl3): d = 5.75 (d, J 1.8 Hz, 1H, C=CH), 5.32 (d, J 1.8 Hz, 1H, C=CH), 1.42–

1.29 (m, 9H, CH2CH2Me), 1.00 (s, 9H, CMe3), 0.97 (t, J 7.4 Hz, 9H, CH2CH2Me), 0.69–0.62 (m, 6H,

CH2CH2Me). From Ref. 18: 1H NMR (300 MHz, CDCl3): d = 5.74 (d, J 2.0 Hz, 1H, C=CH), 5.31 (d,

J 2.0 Hz, 1H, C=CH), 1.44–1.27 (m, 9H, CH2CH2Me), 0.98 (s, 9H, CMe3), 0.95 (t, J 7.2 Hz, 9H,

CH2CH2Me), 0.69–0.62 (m, 6H, CH2CH2Me).

(E)-(Styryl)triisopropylsilane (VS7a).18, 20 This compound identified as a major

product alongside the (1-phenylvinyl)triisopropylsilane (VS7b). Prepared: 1H

NMR (400.13 MHz, CDCl3): d = 7.82 (d, J 7.6 Hz, 2H, CH-aryls), 7.34 (t, J 7.6

Hz, 2H, CH-aryl), 7.26 (d, J 7.6 Hz, 1H, CH-aryl), 6.95 (d, J 19.2 Hz, 1H, C=CH), 6.39 (d, J 19.2 Hz,

1H, C=CH), 1.25–1.15 (m, 3H, CHMe2), 1.10 (d, J 7.0 Hz, 18H, CHMe2). From Ref. 18, 20: 1H NMR

(500 MHz, CDCl3): d = 7.84 (d, J 7.4 Hz, 2H, CH-aryls), 7.36 (t, J 7.6 Hz, 2H, CH-aryl), 7.28 (d, J

8.6 Hz, 1H, CH-aryl), 6.96 (d, J 19.4 Hz, 1H, C=CH), 6.42 (d, J 19.4 Hz, 1H, C=CH), 1.27–1.17 (m,

3H, CHMe2), 1.12 (d, J 7.0 Hz, 18H, CHMe2).

(1-Phenylvinyl)triisopropylsilane (VS7b).18 This compound was only identified in

solution as a minor product alongside with (E)-(styryl)triisopropylsilane (VS7a);

only selected signals were assigned. Prepared: 1H NMR (400.13 MHz, CDCl3): d =

5.93 (d, J 2.9 Hz, 1H, C=CH), 5.66 (d, J 2.9 Hz, 1H, C=CH). From Ref. 18: 1H NMR (300 MHz,

CDCl3): d = 7.6–7.1 (m, 5H, CH-aryls), 5.89 (d, J 3.0 Hz, 1H, C=CH), 5.66 (d, J 3.0 Hz, 1H, C=CH),

1.1–1.0 (m, 21H, CHMe2 + CHMe2).

S24

(E)-(4-(tert-Butyl)styryl)triisopropylsilane (VS8a).18 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.43 (d, J 8.5Hz, 2H, CH-aryls), 7.36 (d, J 8.5Hz,

2H, CH-aryls), 6.95 (d, J 19.5 Hz, 1H, C=CH), 6.37 (d, J 19.5 Hz, 1H,

C=CH), 1.35 (s, 9H, CMe3), 1.1–1.0 (m, 21H, CHMe2). From Ref. 18: 1H

NMR (300 MHz, CDCl3): d = 7.43 (d, J 8.5Hz, 2H, CH-aryls), 7.36 (d, J 8.5Hz, 2H, CH-aryls), 6.94

(d, J 19.5 Hz, 1H, C=CH), 6.36 (d, J 19.5 Hz, 1H, C=CH), 1.35 (s, 9H, CMe3), 1.1–1.0 (m, 21H,

CHMe2).

(1-(4-(tert-Butyl)phenyl)vinyl)triisopropylsilane (VS8b).18 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.30 (d, J 8.1 Hz, 2H, CH-aryls), 7.08 (d, J 8.2 Hz, 2H,

CH-aryls), 5.91 (d, J 3.1 Hz, 1H, C=CH2), 5.63 (d, J 3.1 Hz, 1H, C=CH2), 1.35 (s,

9H, CMe3), 1.1–1.0 (m, 21H, CHMe2). From Ref. 18: 1H NMR (300 MHz, CDCl3):

d = 7.31 (d, J 8.2Hz, 2H, CH-aryls), 7.10 (d, J 8.2Hz, 2H, CH-aryls), 5.90 (d, J 3.2 Hz, 1H, C=CH2),

5.64 (d, J 3.2 Hz, 1H, C=CH2), 1.34 (s, 9H, CMe3), 1.2–1.1 (m, 21H, CHMe2).

(E)-(3,3-Dimethylbut-1-en-1-yl)triisopropylsilane (VS9a).21 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 6.03 (d, J 19.2 Hz, 1H, C=CH), 542 (d, J 19.2 Hz, 1H,

C=CH), 1.1–1.0 (m, 30H, CMe3 + CHMe2). From Ref. 21: 1H NMR (300 MHz,

CDCl3): d = 6.07 (d, J 19.0 Hz, 1H, C=CH), 5.37 (d, J 19.0 Hz, 1H, C=CH), 1.1–1.0 (br m, 30H, CMe3

+ CHMe2).

(3,3-Dimethylbut-1-en-2-yl)triisopropylsilane (VS9b).18 This compound was only

identified in solution as a minor component in a mixture with (E)-(3,3-dimethylbut-

1-en-1-yl)triisopropylsilane (HS9a). Prepared: 1H NMR (400.13 MHz, CDCl3): d = 5.72 (d, J 2.4 Hz,

1H, C=CH), 5.29 (d, J 2.4 Hz, 1H, C=CH), 1.2–1.0 (br m, 30H, CMe3 + CHMe2). From Ref. 18: 1H

NMR (300 MHz, CDCl3): d = 6.07 (d, J 19.0 Hz, 1H, C=CH), 5.37 (d, J 19.0 Hz, 1H, C=CH), 1.00

(br m, 30H, CMe3 + CHMe2).

S25

(E)-(Styryl)dimethylphenylsilane (VS10a).17b, 20, 22 Prepared: 1H NMR (400.13

MHz, CDCl3): d = 7.6–7.5 (m, 2H, CH-aryls), 7.5–7.4 (m, 2H, CH-aryls), 7.4–

7.3 (m, 6H, CH-aryls), 6.96 (d, J 19.1 Hz, 1H, C=CH), 6.60 (d, J 19.1 Hz, 1H,

C=CH), 0.49 (s, 6H, Me). From Ref. 22c: 1H NMR (300 MHz, CDCl3): d = 7.6–

7.2 (m, 5H, CH-aryls), 7.0 (d, J 19.0 Hz, 1H, C=CH), 6.6 (d, J 19.0 Hz, 1H, C=CH), 0.36 (s, 6H, Me).

(1-Phenylvinyl)dimethylphenylsilane (VS10b).17b, 22b, 22c, 23 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.6–7.3 (m, 5H, CH-aryls), 6.01 (d, J 2.9 Hz, 1H, C=CH),

5.69 (d, J 2.9 Hz, 1H, C=CH), 0.41 (s, 6H, Me). From Ref. 22b: 1H NMR (500 MHz,

CDCl3): d = 7.77–7.34 (m, 5H, CH-aryls), 6.20 (s, 1H, C=CH2), 5.88 (s, 1H,

C=CH2), 0.41 (s, 6H, Me).

(E)-(4-(tert-Butyl)styryl)dimethylphenylsilane (VS11a).22a, 24 Prepared: 1H

NMR (400.13 MHz, CDCl3): d = 7.6–7.5 (m, 3H, CH-aryls), 7.5–7.3 (m,

6H, CH-aryls), 6.95 (d, J 19.2 Hz, 1H, C=CH), 6.56 (d, J 19.2 Hz, 1H,

C=CH), 1.33 (s, 9H, CMe3), 0.44 (s, 6H, SiMe2). From Ref. 24: 1H NMR

(400 MHz, CDCl3): d = 7.57 (dd, J 6.4 Hz, 3.0 Hz, 2H, CH-aryls), 7.42 –

7.33 (m, 7H, CH-aryls), 6.93 (d, J 19.1 Hz, 1H, C=CH), 6.54 (d, J 19.1 Hz, 1H, C=CH), 1.32 (s, 9H,

CMe3), 0.42 (s, 6H, SiMe2).

(1-(4-(tert-Butyl)phenyl)vinyl)dimethylphenylsilane (VS11b).18, 22a, 25 Prepared:

1H NMR (400.13 MHz, CDCl3): d = 7.7–7.2 (m, 9H, CH-aryls), 6.03 (d, J 2.8 Hz,

1H), 5.66 (d, J 2.8 Hz, 1H), 1.33 (s, 9H, CMe3), 0.49 (s, 6H, SiMe2). From Ref. 25:

1H NMR (300 MHz, CDCl3): d = 6.04 (d, J 2.8 Hz, 1H, C=CH2), 5.66 (d, J 2.8 Hz,

1H, C=CH2).

S26

(E)-(3,3-Dimethylbut-1-en-1-yl)dimethylphenylsilane (VS12a).17b, 18, 26

Prepared: 1H NMR (400.13 MHz, CDCl3): d = 7.6–7.3 (m, 5H, CH-aryls), 6.94

(d, J 19.0 Hz, 1H, C=CH), 6.55 (d, J 19.0 Hz, 1H, C=CH), 1.33 (s, 9H, CMe3),

0.43 (s, 6H, SiMe2). From Ref. 26: 1H NMR (300 MHz, CDCl3): d = 7.54–7.29

(m, 5H, CH-aryls), 6.13 (d, J 19.0 Hz, 1H, C=CH), 5.65 (d, J 19.0 Hz, 1H, C=CH), 1.01 (s, 9H, CMe3),

0.31 (s, 6H, SiMe2).

(3,3-Dimethylbut-1-en-2-yl)dimethylphenylsilane (VS12b).17b, 18, 27 Prepared: 1H

NMR (400.13 MHz, CDCl3): d = 7.6–7.3 (m, 5H, CH-aryls), 6.04 (d, J 2.7 Hz, 1H,

C=CH), 5.66 (d, J 2.7 Hz, 1H, C=CH), 1.30 (s, 9H, CMe3), 0.42 (s, 6H, SiMe2).

From Ref. 27: 1H NMR (300 MHz, CDCl3): d = 7.6–7.3 (m, 5H, CH-aryls), 5.80 (d,

J 1.9 Hz, 1H, C=CH), 5.41 (d, J 1.91 Hz, 1H, C=CH), 1.02 (s, 9H, CMe3), 0.42 (s, 6H, SiMe2).

(E)-(1,2-diphenylvinyl)triethylsilane (VS13).28 Prepared: 1H NMR (400.13

MHz, CDCl3): d = 7.26–7.19 (m, 3H, CH-aryls), 7.14–7.09 (m, 3H, CH-aryls),

7.03–7.00 (m, 4H, CH-aryls), 6.75 (s, 1H, C=CH), 0.88 (t, J 8.1 Hz, 9H, CH2Me),

0.58 (q, J 7.9 Hz, 6H, CH2Me). From Ref. 28: 1H NMR (300 MHz, CDCl3): d = 7.33–7.15 (m, 3H),

7.13–7.05 (m, 3H), 7.02–6.91 (m, 4H), 6.77 (s, 1H), 0.95 (t, J 7.9 Hz, 9H), 0.65 (q, J 7.9 Hz, 6H).

(E)-(1,2-diphenylvinyl)dimethyl(phenyl)silane (VS14).28 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.47–7.43 (m, 2H, CH-aryls), 7.28–7.25 (m, 3H,

CH-aryls), 7.17–7.07 (m, 3H, CH-aryls), 7.00–6.94 (m, 3H, CH-aryls), 6.86–

6.79 (m, 4H, CH-aryls), 6.74 (s, 1H, C=CH), 0.39 (s, 6H, SiMe2). From Ref. 28:

1H NMR (300 MHz, CDCl3): d = 7.58–7.51 (m, 2H), 7.39–7.31 (m, 3H), 7.27–7.16 (m, 3H), 7.10–

7.04 (m, 3H), 6.97–6.86 (m, 4H), 6.82 (s, 1H), 0.39 (s, 6H).

HEt3Si

HSi

S27

(E)-triethyl(oct-4-en-4-yl)silane (VS15).29 Prepared: 1H NMR (400.13 MHz,

CDCl3): d = 5.67 (t, J 6.9, 1H), 2.04 (dt, J 7.1, 7.1, 2H), 2.07–2.02 (m, 2H), 1.41

(tq, J 7.3, 7.3 Hz, 2H), 1.36–1.23 (m, 2H), 0.86–0.80 (m, 15H), 0.58 (q, J 7.7 Hz, 6H, CH2Me). From

Ref. 29: 1H NMR (300 MHz, CDCl3): d = 5.67 (t, J 6.9 Hz, 1H), 2.09 (dt, J 6.9 Hz, 7.2 Hz, 2H), 2.07–

2.02 (m, 2H), 1.40 (tq, J 7.2 Hz, 7.2 Hz, 2H), 1.36–1.23 (m, 2H), 0.94–0.89 (m, 15H), 0.57 (q, J 7.5

Hz, 6H).

(E)-dimethyl(oct-4-en-4-yl)(phenyl)silane (VS16).30 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.47–7.37 (m, 2H, CH-aryls), 7.37–7.28 (m, 3H,

CH-aryls), 5.78 (t, J 6.8 Hz, 1H, C=CH), 2.10–2.02 (m, 4H, CH2(C=)), 1.37 (q,

J 7.3 Hz, 2H, CH2CH2(C=)), 1.23 (q, J 7.8 Hz, 2H, CH2CH2(C=)), 0.91 (t, J 7.2

Hz, 3H, MeCH2), 0.88 (t, J 7.3 Hz, 3H, MeCH2), 0.79 (t, J 7.3 Hz, 3H, MeCH2), 0.30 (s, 6H, SiMe2).

From Ref. 30: 1H NMR (400 MHz, CDCl3): d = 7.51–7.49 (m, 2H, CH-aryls), 7.34–7.31 (m, 3H, CH-

aryls), 5.80 (t, J 6.7 Hz, 1H, C=CH), 2.12–2.06 (m, 4H, CH2(C=)), 1.40 (q, J 7.2 Hz, 2H,

CH2CH2(C=)), 1.23 (q, J 7.6 Hz, 2H, CH2CH2(C=)), 0.91 (t, J 7.2 Hz, 3H, MeCH2), 0.91 (t, J 7.2 Hz,

3H, MeCH2), 0.82 (t, J 7.2 Hz, 3H, MeCH2), 0.32 (s, 6H, SiMe2).

Major component (E)-triethyl(1-phenylprop-1-en-1-yl)silane

(VS17a).31 Prepared: 1H NMR (400.13 MHz, CDCl3): d = 7.28

(t, J 7.6 Hz, 1H, CH-aryls), 7.15 (tt, J 7.6 Hz, 1.3 Hz, 1H, CH-

aryls), 6.93 (dd, J 7.6 Hz, 1.3 Hz, 2H, CH-aryls), 6.07 (q, J 6.6 Hz, 1H, C=CH), 1.57 (d, J 6.6 Hz, 3H,

C=CMe), 0.91 (t, J 7.8 Hz, 9H, CH2Me), 0.55 (q, J 7.8 Hz, 6H, CH2Me). From Ref. 31: 1H NMR (400

MHz, CDCl3): d = 7.29 (t, J 7.8 Hz, 2H, CH-aryls), 7.16 (t, J 7.8 Hz, 1H, CH-aryls), 6.94–6.91 (m,

2H, CH-aryls), 6.06 (q, J 6.5 Hz, 1H, C=CH), 1.57 (d, J 6.6 Hz, 3H, C=CMe), 0.90 (t, J 7.9 Hz, 9H,

CH2Me), 0.55 (q, J 7.9 Hz, 6H, CH2Me). For minor component (E)-triethyl(1-phenylprop-1-en-2-

yl)silane (VS17b)31a only selected signals were assigned in mixture with VS17a: Prepared: 1H NMR

(400 MHz, CDCl3): d = 6.77 (s, br, 1H, C=CH), 1.94 (d, J 1.6 Hz, 3H, C=CMe), 0.98 (t, J 7.9 Hz, 9H,

HEt3Si

HSi

HEt3Si SiEt3H

S28

CH2Me), 0.69 (q, J 7.9 Hz, 6H, CH2Me). From Ref. 31: 1H NMR (500 MHz, CDCl3): d = 6.72 (s, 1H,

C=CH), 1.95 (s, 3H, C=CMe).

Compounds analyzed as a mixture. (E)-dimethyl(phenyl)(1-

phenylprop-1-en-1-yl)silane (VS18a).32 Prepared: 1H NMR

(400.13 MHz, CDCl3): d = 7.80–7.10 (m, br, 10H, CH-

aryls), 6.21 (q, br, J 6.6 Hz, 1H, C=CH), 1.66 (d, J 6.4 Hz,

3H, C=CMe), 0.41 (s, 6H, SiMe2). From Ref. 32: 1H NMR (300 MHz, CDCl3): d = 7.28 (m, 10H, CH-

aryls), 6.22 (q, J 6.6 Hz, 1H, C=CH), 1.68 (d, J 6.6 Hz, 3H, C=CMe), 0.40 (s, 6H, SiMe2). (E)-

dimethyl(phenyl)(1-phenylprop-1-en-2-yl)silane (VS18b).32 Prepared: 1H NMR (400 MHz, CDCl3): d

= 7.80–7.10 (m, br, 10H, CH-aryls), 6.91 (s, br, 1H, C=CH), 2.04 (s, 3H, C=CMe), 0.53 (s, 6H, SiMe2).

From Ref. 32: 1H NMR (300 MHz, CDCl3): d = 7.35 (m, 10H, CH-aryls), 6.86 (q, J 1.8 Hz, 1H, C=CH),

2.04 (d, J 1.8 Hz, 3H, C=CMe), 0.43 (s, 6H, SiMe2).

HSi SiH

S29

Experimental NMR spectra of the hydrosilylation mixtures containing silylated

products

Some of the representative spectra provided herein contain 1,2-dimethoxyethane added as standard for

the quantification purpose; resonances due to standard added appear at 3.40 (s, 6H, Me) and 3.55 (s,

4H, CH2) ppm. Residual toluene (solvent for the catalytic runs) is also presented in some reaction

mixtures. Peak assignments and integration values are provided on pages S20–S28.

S47

Hypothetic mechanism of the catalytic cycle

Initial experiments. Attempts to shed some light on the mechanism of photocatalytic action of [2] and

[3] were undertaken. Thus, in the first set of experiments, model catalytic system with catalysts [2] or

[3] was irradiated for a shorter period of time (1 h, entries B11, B13, C13, and C15, Table S4) and the

reaction was allowed to continue in the darkness. Lower yields of silylated products were achieved in

all these experiments, and those were consistent with the results obtained for the same reaction to run

for 1 h only. This suggests that the irradiation with visible light is crucial throughout the entire reaction

course and excludes the possibility for the light to be solely responsible for the initial generation of

catalytically active species as known for the UV-light-induced hydrosilylations.33 Catalytic run with

[2] or [3] in the presence of metallic mercury (mercury drop test11b) showed similar results to those in

the absence of mercury; reaction rate or product yields were unaffected. Accumulation of products in

the initial period (up to 2 h at 60 °C) followed a nearly linear time-dependence with no induction period

observed. These experiments suggest that no formation of nanoparticles or ligand-free metal clusters34

occur and that a molecular catalytic cycle under homogeneous conditions could be expected.35

In the second set of experiments, we followed the hydrosilylation of phenyl acetylene with

triethylsilane at 40 °C in toluene using catalysts [2] or [3] (1 mol% catalyst loading) by ESI/MALDI-

MS, IR and 1H NMR spectroscopy. After 1 h under visible light irradiation, we detected the presence

of xylyl isocyanide in the reaction mixture. This was identified by IR (an aliquot from reaction mixture

was evaporated to dryness and IR spectrum was recorded on ATR-IR instrument; found ν(CºN) 2120;

from Ref. 36: 2122), MALDI-MS [an aliquot from reaction mixture was spiked with DCTB matrix in

MeOH and placed on MALDI plate; found 150.091 [M + H3O]+, calcd for C9H12NO 150.0919], and

HR-ESI-MS [an aliquot from reaction mixture was diluted with MeOH and injected into the ESI mass-

spectrometer, 150.0915 [M + H3O]+, calcd for C9H12NO 150.0919]. Only traces of isocyanide were

detected in the reaction without irradiation with light. Noteworthy, UV-light-induced dissociation of

S48

the isocyanide ligands from metal centre to generate catalytically active species was previously

observed by Jones and co-workers.37

Inspection of the MALDI spectra of the same reaction mixture with [2] after 1 h allowed for

the detection of several key signals with characteristic platinum isotopic distribution (Table S7).

Structures of corresponding compounds were tentatively assigned as: C1, product of the oxidative

addition of silane to the activated metal core containing one bidentate carbene ligand, found 537.1 [M

+ H]+, calcd for C20H32N3PtSi 537.2; and C2, product of the migratory insertion of alkyne, found 639.3,

calcd for C28H38N3PtSi 639.3. Related ions were also found in ESI-MS spectra although their intensity

was very low. In both C1 and C2, platinum centre has an oxidation state of II, that is consistent with

the initial loss of the isocyanide and chloride ligands from the starting pre-catalyst [2] and the reduction

of the metal centre to platinum(0).

Table S7. Plausible intermediates of the catalytic cycle detected by the ESI-MS and MALDI-MS

techniques.

C1

MALDI-MS: found 537.1 [M + H]+, calcd for

C20H32N3PtSi 537.2

ESI-MS: found 559.1837 [M + Na]+, calcd for

C20H31N3NaPtSi 559.1833

C2

MALDI-MS: found 639.2 [M + H]+, calcd for

C28H38N3PtSi 639.3.

ESI-MS: found 702.2560 [M + MeCN + Na]+,

calcd for C30H40N4NaPtSi 702.2564.

We also attempted to trace the origin of the reducing agent for the catalyst core. When the

solution of [2] was heated at 40 °C in toluene for 1 h either with or without light, no reduction of [2]

PtC N

H

XylSiEt3

N

NH

H

PtC N

H

XylSiEt3

N

NH

Ph H

H

S49

was detected by ESI-MS and 1H NMR. No reduction was also observed when a solution of catalyst

[2] (1 mol%) was heated at 40 °C for 1 h in the presence of phenylacetylene either with or without

light. When a solution of [2] (1 mol%) with triethyl silane were heated at 40 °C for 1 h under visible

light irradiation, disappearance of the strong signal due to [M + H] for starting [2] in the ESI-MS was

observed; isocyanide was also detected in the reaction mixture as explained above. When the reaction

was undertaken in the darkness, changes in mass- or IR spectra were insignificant, and only traces of

isocyanide were detected. Although we were unable to establish the structure of compounds formed in

these reduction experiments, the subsequent addition of phenylacetylene to the latter reaction mixture

led to the observation of peaks of C2 in the mass-spectra. These experiments suggest that small amount

of silane substrate plays a role of the sacrificial reducing agent for the metal centre leading to the

generation of the catalytically active species. At this point, we believe that light accelerates the

dissociation of the isocyanide ligands from [2] making it more prone to the subsequent reduction.

Corresponding UV-light-induced dissociation of the isocyanide ligands to generate catalytically active

species were previously observed by Jones and co-workers.37 UV-Vis spectra after the reduction

experiment corresponds to that one for the catalytic mixture after catalysis, where some of the

absorbance of the solution in the region 400–450 nm is retained (Figure S3).

Proposed catalytic cycle. Taking all these experiments into account, we proposed the

mechanism of the photocatalytic cycle with catalyst [2] (see Figure S4 for reaction of terminal alkyne)

on basis of Chalk-Harrod mechanism. It includes the oxidative addition of silane, p-coordination of

alkyne, its 1,2-migratory insertion either into Pt–H or Pt–Si bond and the reductive elimination of

corresponding silylated products.38 Additional studies with deuterated silane (see below) confirm the

key 1,2-migratory insertion step for both terminal and internal alkyne insofar as deuterium from Et3SiD

was always located on alkene carbon vicinal to the silyl group. We believe that similar mechanism

S50

should be valid for the reaction with either internal or terminal alkynes as intermediate C1 was

observed in MALDI/ESI-MS spectra of either reaction mixture.

In our hypothesis, irradiation with the visible light facilitates the removal of the isocyanide

ligand followed by the reduction of metal core by a sacrificial amount of silane substrate. Oxidative

addition of silane leads to the product of the type C1, that requires one additional vacancy at metal

core for the subsequent alkyne binding.

Figure S4. Proposed mechanism of the catalytic cycle involving platinum-ADC catalyst [2].

Oxidative addition

CCR1 H

Reductive elimination Light-accelerated

dissociation of the isocyanide and

reduction of metal cente by silane

Migratory insertion and pyridyl coordination

PtC

NHXyl

Cl

CN

Xyl

N

NH

Cl

(pre)-catalyst [2]

–2Cl–

–CNXyl

HSiR3

Light-driven dissociation of the pyridyl moiety followed by π-coordination of alkyne

PtC

NHXyl

H

N

NHSiR3

CC

R1

H

H

HR1

SiR3

only formation of β-(E) isomer is shown

only pathway leading to β-(E) isomer through insertion of alkyne into Pt–H bond is shown

C1C2

[Pt]CN

H

XylN

NH

PtC N

H

XylSiR3

N

NH

H

PtC N

H

XylSiR3

N

NH

R1 H

H

S51

It could be achieved via the reversible visible-light-mediated dissociation of the pyridyl moiety

of the bidentate aminocarbene ligand in a similar way as reported by Turro and co-workers39 for the

photo-dissociation of pyridyl ligands at ruthenium centre upon visible light irradiation at 450 nm. In

our case, dissociation of the pyridyl moiety of the ADC ligand will change a binding mode of the

aminocarbene ligand from C,N-bidentate to a C-monodentate, potentially facilitating the substrate

binding in the course of catalysis. Insofar as the visible-light-mediated dissociation of the pyridyl-

ligand are reversible in nature, continuous irradiation with light is essential to govern this process.

Similar pathways can be described for [3], however, further studies, including DFT calculations are

required before more definitive conclusions could be withdrawn for mechanism of photocatalytic

action of [2] and, in particular for [3], where additional influence of the secondary metal centre should

be carefully considered.

Additional control experiments using deuterated silane. Deuterated triethylsilane, Et3SiD was

used in the model catalytic reactions with either phenyl- (reaction D1) or diphenylacetylene (reaction

D2) as alkynes and representative catalyst [2]; other reactions conditions were as described in Tables

2 and 3. Upon completion, the reaction mixtures were evaporated to dryness, re-dissolved in CDCl3 or

CHCl3, and analysed by 1H and 2H NMR spectroscopy, correspondingly. Stack plots of the

corresponding NMR spectra are provided below (Figures S5 and S6).

When terminal alkyne (reaction D1, Figure S5) was used, in both a and b-(E) vinylsilanes

formed, one of the alkene hydrogens was replaced with the deuterium. For b-(E) isomer, this deuterium

atom is located at the alkene carbon vicinal with respect to the silane group.

S52

Figure S5. Additional control experiments using Et3SiD as silane, phenylacetylene, and catalyst [2].

Legend: a) bottom 1H NMR spectrum corresponds to the control experiment with non-deuterated silane

and 1,4-dimethoxyethane as standard; b) top 1H NMR spectrum corresponds to the reaction mixture

using Et3SiD and phenylacetylene; one in each pair of hydrogens of alkene moiety from a and b(E)-

vinylsilanes generated is replaced with deuterium; c) middle 2H spectrum shows the deuteration sites

for each of two vinylsilane products.

For internal alkyne (reaction D2, Figure S6), a sole alkene hydrogen was replaced with the

deuterium.

In all the reactions, no hydrogen/deuterium scrambling was observed even after 60 °C for 12 h

with either deuterated or non-deuterated toluene as solvent. We also noted that reaction rates for Et3SiD

and Et3SiH were nearly identical suggesting that oxidative addition of silane is not a rate limiting step.

S53

Figure S6. Additional control experiments using Et3SiD as silane, diphenylacetylene, and catalyst [2].

Legend: a) bottom 1H NMR spectrum corresponds to the control experiment using non-deuterated

silane and 1,4-dimethoxyethane as standard; b) top 1H NMR spectrum belongs to the reaction mixture

of Et3SiD with diphenylacetylene; hydrogen of alkene moiety is replaced with deuterium; c) middle

2H spectrum shows the deuteration site for the vinylsilane formed.

S54

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