Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 SUPPORTING INFORMATION FOR Does the rate of competing isomerisation during alkene metathesis depend on pre-catalyst initiation rate? David J. Nelson* and Jonathan M. Percy* WestCHEM Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK Contents General Experimental S2 Kinetic Data Plots 1,8-nonadiene 3 mol% G1 benzene-d6 (Figure 1) S3 1,8-nonadiene 3 mol% G2 benzene-d6 (Figure 2) S4 1,8-nonadiene 3 mol% GH2 benzene-d6 (Figure 3) S5 1,8-nonadiene 3 mol% Zhan1B benzene-d6 (Figure 3) S6 1,8-nonadiene 3 mol% Grela2 benzene-d6 (Figure 3) S7 1,8-nonadiene 3 mol% M853-SIPr benzene-d6 (Figure 4) S8 1,8-nonadiene 3 mol% G2 chloroform-d (Figure 5) S9 1,8-nonadiene 3 mol% G2 undried chloroform-d S10 1,8-nonadiene 3 mol% G2 DCM-d2 (Figure 5) S11 1,8-nonadiene 3 mol% G2 toluene-d8 (Figure 5) S12 Cycloheptene 3 mol% G2 benzene-d6 (Figure 6) S13 Cycloheptene/1,7-octadiene 3 mol% G2 benzene-d6 S14 Initiation rate measurement for Zhan1B S15 References S15 S1 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 General Experimental Kinetic data were acquired using a Bruker Avance II spectrometer (600 MHz 1H observe frequency), equipped with TBI-z probe (inverse 1H/13C/BB) and temperature control. All kinetic experiments were acquired at 298 K, with an interpulse delay of 35 s to ensure accurate quantification; relaxation times for signals corresponding to many components in the reaction mixtures are known to be up to ca. 7 s.1 Data were processed using Bruker Topspin (version 2.1 or 3.0) and Microsoft Excel (2007 or 2010). Complexes G1, G2 and GH2 were purchased from Sigma Aldrich and used as supplied. Zhan1B and Grela2 were purchased from Strem. M853-SIPr was supplied by Omega Cat System (Rennes, France). Benzene-d6, chloroform-d and toluene-d8 were purchased from Sigma Aldrich, and dichloromethane-d2 was purchased from Goss Scientific. Deuterated solvents were dried on activated 4 Å molecular sieves overnight and degassed with a stream of nitrogen or argon, unless otherwise stated. 1,8-Nonadiene was purchased from Sigma Aldrich and passed through a pad of activated alumina before use. S2 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 Kinetic Data Plots 1,8-nonadiene 3 mol% G1 benzene-d6 (Figure 1) Cycloheptene Ethene 120 100 80 60 40 Concentration / mM 20 0 0 5000 10000 15000 20000 Time /s Pre-Catalyst Alkylidene Methylidene 12 10 8 6 4 Concentration / mM 2 0 0 5000 10000 15000 20000 Time /s ln[Alkylidene] Linear (ln[Alkylidene]) -4.0 -4.5 -5.0 -5.5 y = -2.78E-04x - 4.54E+00 R² = 9.94E-01 -6.0 ln[Alkylidene] -6.5 -7.0 -7.5 0 1000 2000 3000 4000 5000 6000 7000 8000 Time /s S3 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% G2 benzene-d6 (Figure 2) Cycloheptene Cyclohexene Ethene Cyclic Dimer 120 100 80 60 40 Concentration / mM 20 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Time /s Pre-Catalyst Alkylidene Methylidene Sum of Ru=CHR 14 12 10 8 6 4 Concentration / mM 2 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Time /s S4 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% GH2 benzene-d6 (Figure 3) Cycloheptene Cyclohexene Cyclic Dimer Ethene 200 180 160 140 120 100 80 60 Concentration / mM 40 20 0 0 2000 4000 6000 8000 10000 Time /s Pre-Catalyst 10 9 8 7 6 5 4 3 Concentration / mM 2 1 0 0 2000 4000 6000 8000 10000 Time /s S5 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% Zhan1B benzene-d6 (Figure 3) Cycloheptene Cyclohexene Ethene Cyclic Dimer 140 120 100 80 60 40 Concentration / mM 20 0 0 1000 2000 3000 4000 5000 6000 7000 8000 Time /s Pre-Catalyst 10 9 8 7 6 5 4 3 Concentration / mM 2 1 0 0 1000 2000 3000 4000 5000 6000 7000 8000 Time /s S6 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% Grela2 benzene-d6 (Figure 3) Cycloheptene Cyclohexene Ethene Cyclic Dimer 140 120 100 80 60 40 Concentration / mM 20 0 0 2000 4000 6000 8000 10000 12000 Time /s Pre-Catalyst 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Concentration / mM 0.5 0.0 0 2000 4000 6000 8000 10000 12000 Time /s S7 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% M853-SIPr benzene-d6 (Figure 4) 300 Cycloheptene Cyclohexene Ethene Cyclic Dimer 250 200 150 100 Concentration / mM Concentration 50 0 0 1000 2000 3000 4000 5000 Time /s S8 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% G2 chloroform-d (Figure 5) Cycloheptene Cyclohexene Cyclic Dimer 45 40 35 30 25 20 15 Concentration / mM 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 Time /s Alkylidene Methylidene Pre-Catalyst 3.0 16 14 2.5 12 2.0 10 1.5 8 6 1.0 4 [PreCatalyst] / mM Concentration / mM 0.5 2 0.0 0 0 2000 4000 6000 8000 10000 12000 14000 16000 Time /s S9 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% G2 undried chloroform-d Cyclohexene Cyclic Dimer Cycloheptene 45 40 35 30 25 20 15 Concentration / mM 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Time /s Alkylidene Methylidene Pre-Catalyst 2.5 16 14 2.0 12 1.5 10 8 1.0 6 Catalyst] / mM - 4 [Pre Concentration / mM 0.5 2 0.0 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Time /s S10 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% G2 DCM-d2 (Figure 5) Cyclohexene Cyclic Dimer Cycloheptene 70 60 50 40 30 20 Concentration /mM 10 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 Time /s Pre-Catalyst Alkylidene Ethylidene Methylidene 14 12 10 8 6 4 Concentration /mM 2 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 Time /s S11 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 1,8-nonadiene 3 mol% G2 toluene-d8 (Figure 5) 120 Cycloheptene Cyclohexene Ethene 100 80 60 40 Concentration / mM 20 0 0 5000 10000 15000 20000 Time /s 14 Pre-Catalyst Alkylidene Methylidene 12 10 8 6 4 Concentration / mM 2 0 0 5000 10000 15000 20000 Time /s S12 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 Cycloheptene 3 mol% G2 benzene-d6 (Figure 6) Cycloheptene Cyclohexene Cyclic Dimer 100 90 1 - 80 70 60 50 40 30 20 Concentration / / Concentration mmol L 10 0 0 2000 4000 6000 8000 10000 12000 14000 Time /s Pre-Catalyst Alkylidene Sum 14 12 10 8 6 4 Concentration / mM 2 0 0 2000 4000 6000 8000 10000 12000 14000 Time /s S13 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 Cycloheptene/1,7-octadiene 3 mol% G2 benzene-d6 Cycloheptene Cyclohexene Ethene Cyclic Dimer 500 450 1 - 400 350 300 250 200 150 100 Concentration / / Concentration mmol L 50 0 0 5000 10000 15000 20000 Time /s Pre-Catalyst Ethylidene + Alkylidene Methylidene Sum 20 18 1 - 16 14 12 10 8 6 4 Concentration / / Concentration mmol L 2 0 0 5000 10000 15000 20000 Time /s S14 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014 Initiation Rate Measurement for Zhan1B The initiation rate for this complex was determined by monitoring the reaction of the pre-catalyst with ethyl vinyl ether in DCM solution at 298 K using UV/visible spectroscopy, using the same apparatus and method used for the 2 3 determination of the initiation rate constants for complexes GH2 and Grela2. -1 -1 [ethyl vinyl ether] / mol L kobs /s 0.02676 0.00336 0.02662 0.00379 0.05055 0.00695 0.05029 0.00705 0.10320 0.01409 0.10267 0.01405 0.20205 0.02626 0.20101 0.02624 0.030 y = 0.132x R² = 0.9982 0.025 1 - / s 0.020 obs 0.015 0.010 Rate Rate Constant k 0.005 0.000 0.00 0.05 0.10 0.15 0.20 0.25 [Ethyl Vinyl Ether] / mol L-1 References 1. I. W. Ashworth, D. Carboni, I. H. Hillier, D. J. Nelson, J. M. Percy, G. Rinaudo and M. A. Vincent, Chem. Commun., 2010, 46, 7145-7147. 2. I. W. Ashworth, I. H. Hillier, D. J. Nelson, J. M. Percy and M. A. Vincent, Chem. Commun., 2011, 47, 5428- 5430. 3. D.