Supporting Information (SI) Heterobimetallic Pd-Sn Catalysis: Michael Addition Reaction with C-, N-, -, S- Nucleophiles and In-situ Diagnostics Debjit Das, a Sanjay Pratihar a,b and Sujit Roy c * a rganometallics & Catalysis Laboratory, Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India b Department of Chemical Sciences, Tezpur University, Napaam,784028, Assam, India c rganometallics & Catalysis Laboratory, School of Basic Sciences, Indian Institute of Technology, Bhubaneswar 751013, India sujitroy.chem@gmail.com, sroychem@iitbbs.ac.in Table of Contents: S-1. Initial Kinetic Study S-2. UV-Visible Study S-3. NMR Study for the Interaction of α,β-unsaturated Ketones S-4. RTEP of 3ca and 3cp S-5. DFT Study S-6. Spectra of All Products 1
S-1. Initial Kinetic Study A mixture of trimethoxy benzene 2a (0.2 mmol), methyl vinyl ketone 1a (0.02 mmol), and catalyst (1 mol %) in 0.5 ml of CDCl 3 and 10 µl of MeCN was taken at room temperature (30 o C) in a NMR tube. Then the tube was subjected for recording 1 H NMR after different time intervals using triphenyl methane (1 mg) as internal standard. Pseudo-first order rate plots 0.8 k PdCl2 (MeCN) 2 = 3.21 x 10-3 s -1 R = 0.986 -log[(c t - C α )/(C 0 - C α )] 0.6 0.4 0.2 0 50 100 150 200 250 300 Time (min) 2
0.5 k SnCl2 = 3.59 x 10-3 s -1 R = 0.993 -log[(c t - C α )/(C 0 - C α )] 0.4 0.3 0.2 0.1 0 20 40 60 80 100 120 140 160 Time (min) 0.5 0.4 k (CD)PdClSnCl3 = 8.25 x 10-3 s -1 R = 0.987 -log[(c t - C α )/(C 0 - C α )] 0.3 0.2 0.1 0 10 20 30 40 50 60 Time (min) 3
-log[(c t - C α )/(C 0 - C α )] 0.4 0.3 0.2 k (NBD)PdClSnCl3 = 10.58 x 10-3 s -1 R = 0.999 0.1 5 10 15 20 25 30 35 40 Time (min) -log[(c t - C α )/(C 0 - C α )] 0.40 0.32 0.24 k (CHD)PdClSnCl3 = 15.36 x 10-3 s -1 R = 0.981 0.16 0 5 10 15 20 25 Time (min) 4
0.35 k (MeCN)2 PdClSnCl 3 = 24.41 x 10-3 s -1 R = 0.985 -log[(c t - C α )/(C 0 - C α )] 0.28 0.21 0.14 2 4 6 8 10 12 14 16 18 Time (min) S-2. UV-Visible Study 1) A solution of 2.5 10-4 M in MeCN/DCM (1:40) of PdCl 2 (MeCN) 2 was prepared and UV- Visible spectra of this solution was recorded at room temperature. 2) A solution of 2.5 10-4 M in MeCN/DCM (1:40) of PdCl 2 (MeCN) 2 and SnCl 2 (1:1) was prepared and UV-Visible spectra of this solution was recorded at room temperature. 3) To this above solution of PdCl 2 (MeCN) 2 (1 equiv.) and SnCl 2 (1 equiv.), 1 equiv. 1,5- cyclooctadiene was added and UV-Visible spectra of final solution was recorded at room temperature. S-3. NMR Study for the Interaction of α,β-unsaturated Ketones with Pd-Sn To see the initial activation the 13 C spectrum of α,β-unsaturated ketone (1b/1i) was recorded in CDCl 3 /MeCN solvent at room temperature in the absence as well as in the presence of PdCl 2 (MeCN) 2 and SnCl 2 catalytic system. 5
Shift in 13 C NMR α,β-unsaturated ketone Catalyst combination Solvent medium Shift of C 1 (ppm) Shift of C 2 (ppm) Shift of C 3 (ppm) (0.05 mmol) PdCl 2 (MeCN) 2 and SnCl 2 (0.05 mmol and 0.05 mmol) CDCl 3 /MeCN (3:1) 800 µl 0.68 0.03 0.79 (0.05 mmol) PdCl 2 (MeCN) 2 and SnCl 2 (0.05 mmol and 0.05 mmol) CDCl 3 /MeCN (3:1) 800 µl 0.37 0.19 0.51 6
S-4. RTEP of 3ca (CCDC-904372) and 3cp (CCDC-904373) RTEP of 3ca and 3cp with 30% thermal ellipsoids (H atoms are excluded for clarity) 7
S-5. DFT Study Electronic energies, electronic states and geometries in Cartesian coordinates (Angstroms), the structures of the following compounds: PdCl 2 (CH 3 CN) 2 E = - -923.8121944 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 46 0-0.000021-0.321580-0.000092 2 17 0-1.653531-1.939107-0.000156 3 7 0-1.527839 1.092626-0.000361 4 7 0 1.527645 1.092796-0.000058 5 6 0 2.509079 1.701498-0.000044 6 6 0-2.509273 1.701329-0.000128 7 6 0-3.766091 2.438654 0.000481 8 6 0 3.765875 2.438856-0.000039 9 1 0-3.833158 3.071860-0.889486 10 1 0-3.834953 3.067135 0.893655 11 1 0-4.600223 1.729734-0.002236 12 1 0 3.833831 3.069685 0.891548 13 1 0 4.600037 1.729966-0.000061 14 1 0 3.833813 3.069724-0.891600 15 17 0 1.653850-1.938858 0.000377 8
SnCl 2 E = -1312.7235059 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 50 0 0.000000 0.000000 0.000000 2 17 0 0.000000 0.000000 2.525978 3 17 0 0.000000 0.000000-2.525978 MVK E = -231.2351876 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0 2.015136-0.104414 0.000110 2 6 0 0.803289-0.667376-0.000191 3 6 0-0.441113 0.163515-0.000062 4 6 0-1.756308-0.594597 0.000158 5 8 0-0.401578 1.383257-0.000128 6 1 0 2.926807-0.694686 0.000134 7 1 0-2.591067 0.108527 0.000305 8 1 0-1.823029-1.245508-0.881337 9 1 0-1.822755-1.245594 0.881599 10 1 0 2.110286 0.978202 0.000809 11 1 0 0.686364-1.749770-0.000576 9
C-1 E = -2433.5873954 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 46 0-1.334468 0.000035 0.083930 2 6 0-1.396496-1.663606 1.566118 3 6 0-1.295938-2.238129 0.297919 4 6 0-0.019843-2.813959-0.183997 5 8 0 1.082820-2.238054-0.083863 6 6 0-0.069939-4.165605-0.830004 7 6 0-1.396601 1.663524 1.566025 8 6 0-1.296058 2.237993 0.297766 9 6 0-0.020002 2.813945-0.184109 10 6 0-0.070206 4.165656-0.829980 11 8 0 1.082711 2.238118-0.084045 12 50 0 1.240848 0.000040 0.062175 13 17 0 3.379748 0.000131-0.869114 14 17 0 0.063127-0.000222-2.266846 15 17 0 1.884337 0.000024 2.387941 16 1 0-0.536085-1.587347 2.224994 17 1 0 0.937484-4.561909-0.964316 18 1 0-0.693214-4.861022-0.258555 19 1 0-0.541856-4.041347-1.815618 20 1 0-2.379436 1.547180 2.011114 10
21 1 0 0.937192 4.561985-0.964406 22 1 0-0.542305 4.041521-1.815521 23 1 0-0.693384 4.861002-0.258337 24 1 0-0.536191 1.587401 2.224922 25 1 0-2.201439 2.577026-0.198985 26 1 0-2.201302-2.577121-0.198885 27 1 0-2.379340-1.547174 2.011164 28 17 0-3.783727-0.000122-0.300350 C-2 E = -2335.1141215 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 46 0 1.347169 0.168497-0.189140 2 6 0 1.392103-1.632846-1.466291 3 6 0 1.675532-2.007093-0.156490 4 6 0 0.661649-2.725558 0.688436 5 8 0-0.500622-2.350927 0.786257 6 6 0 1.152182-3.959680 1.400167 7 50 0-1.266121-0.040296-0.073935 8 17 0-2.107497 2.064170-0.893952 9 17 0-2.291837-0.057940 2.049931 10 17 0-2.432324-1.470327-1.560968 11
11 1 0 0.420578-1.828014-1.912803 12 1 0 0.318252-4.462937 1.891467 13 1 0 1.650296-4.641419 0.700605 14 1 0 1.900583-3.667256 2.148957 15 1 0 2.715374-2.082150 0.151610 16 1 0 2.207940-1.380346-2.137235 17 17 0 3.764214 0.370495-0.264478 18 7 0 1.104095 2.142539 0.372936 19 6 0 0.916662 3.261891 0.584092 20 6 0 0.662617 4.671684 0.837786 21 1 0-0.221140 4.981334 0.271072 22 1 0 1.526677 5.269215 0.532519 23 1 0 0.476082 4.826023 1.905125 C-3 E = -2467.8763272 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 46 0-1.116209 0.746161-0.132578 2 6 0-0.469805 1.983255-1.735955 3 6 0-0.083406 2.583721-0.508318 4 6 0 1.354186 2.629580-0.118528 5 8 0 2.088647 1.640632-0.132057 12
6 6 0 1.906811 3.977101 0.268969 7 50 0 1.137955-0.615161-0.238598 8 17 0 0.502333-2.958640-0.194314 9 17 0 2.496661-0.743642 1.716365 10 17 0 2.437410-0.697986-2.220332 11 1 0 0.269173 1.508598-2.377105 12 1 0 2.977230 3.902920 0.465952 13 1 0 1.715017 4.713496-0.520309 14 1 0 1.386591 4.331871 1.168355 15 1 0-0.714845 3.373425-0.109930 16 1 0-1.387201 2.313500-2.212536 17 17 0-3.160063 2.084709 0.049936 18 7 0-1.159101-0.035713 2.021699 19 6 0-0.936543-0.510753 3.052305 20 6 0-0.613730-1.122188 4.334764 21 1 0 0.451459-1.375441 4.346106 22 1 0-1.201133-2.034671 4.473739 23 1 0-0.831111-0.427281 5.151404 24 7 0-2.259770-1.062773-0.760187 25 6 0-2.741301-2.051814-1.111191 26 6 0-3.307924-3.322579-1.541731 27 1 0-4.156396-3.592161-0.905728 28 1 0-2.537489-4.096738-1.466321 29 1 0-3.648018-3.251948-2.579311 13
(CHD)PdClSnCl 3 E = -2204.5363413 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0-3.063330 1.338128 1.223977 2 6 0-3.939482 0.071877 1.102786 3 6 0-4.179358-0.353965-0.324860 4 6 0-3.428614 0.079441-1.363849 5 6 0-2.285236 0.973876-1.148674 6 6 0-2.031110 1.473814 0.125795 7 46 0-1.029872-0.526040-0.170215 8 17 0 0.135002-2.503639 0.287987 9 1 0-3.699650 2.235293 1.154353 10 1 0-2.587566 1.379511 2.208443 11 1 0-3.473529-0.768436 1.641302 12 1 0-4.900782 0.234454 1.604961 13 1 0-1.731803 1.345237-2.006772 14 1 0-1.272260 2.242287 0.242387 15 1 0-3.625907-0.270431-2.372818 16 1 0-4.980114-1.067558-0.505960 17 50 0 1.407451 0.160535 0.015547 18 17 0 1.443305 2.470850-0.554819 19 17 0 2.977247-0.723724-1.465777 20 17 0 2.317149 0.129553 2.167644 14
(NBD)PdClSnCl 3 E = -2242.6040113 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0 2.037170 1.259187-0.695021 2 6 0 2.036152 1.260088 0.692038 3 6 0 3.309889-0.845264-0.678689 4 6 0 3.308877-0.844513 0.680284 5 1 0 1.385380 1.834076-1.342265 6 1 0 1.383363 1.835854 1.337496 7 1 0 3.284563-1.702749-1.341075 8 1 0 3.282465-1.701175 1.343669 9 6 0 3.381540 0.629062 1.130869 10 6 0 3.383295 0.627614-1.131012 11 6 0 4.295497 1.194003 0.000244 12 1 0 3.667241 0.801165 2.167941 13 1 0 3.670486 0.798432-2.167886 14 1 0 5.301211 0.760081 0.001321 15 1 0 4.356288 2.287673-0.000365 16 50 0-1.518911 0.204478-0.000214 17 17 0-2.833789-0.281201-1.874409 18 17 0-2.816060-0.268241 1.890012 19 17 0-1.424289 2.590098-0.009711 20 17 0-0.173405-2.610317-0.001689 15
21 46 0 0.919745-0.546394-0.001127 (CD)PdClSnCl 3 E = -2283.1612003 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 50 0-1.624140 0.128859 0.015985 2 46 0 0.882349-0.407130-0.057482 3 17 0-1.846736 2.497837 0.273858 4 17 0-2.878965-0.281191-1.921876 5 17 0-2.871793-0.677633 1.828379 6 17 0-0.106819-2.534888-0.226126 7 6 0 1.656361 1.612368-0.659753 8 1 0 0.772478 2.118486-1.045785 9 6 0 1.761676 1.540887 0.722431 10 1 0 0.931878 1.968832 1.281331 11 6 0 3.254387-0.947102-0.686548 12 1 0 3.055519-1.778602-1.360634 13 6 0 2.728291 1.352715-1.695793 14 1 0 3.209618 2.309605-1.951102 15 1 0 2.223991 1.023101-2.611912 16 6 0 3.075672-1.179766 0.645418 17 1 0 2.784416-2.188917 0.931113 18 6 0 3.811856 0.313692-1.315922 19 1 0 4.557823 0.764511-0.656259 16
20 1 0 4.345652 0.036701-2.231557 21 6 0 3.029735 1.264466 1.520937 22 1 0 3.880746 1.732067 1.017276 23 1 0 2.936894 1.772177 2.486624 24 6 0 3.322347-0.231244 1.799341 25 1 0 4.359572-0.336712 2.151156 26 1 0 2.691692-0.562436 2.632013 CHD E = -233.4189108 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0 0.047034 1.425712 0.113710 2 6 0-0.047034 0.732084 1.260241 3 6 0 0.047034-0.732084 1.260241 4 6 0-0.047034-1.425712 0.113710 5 6 0-0.295928-0.710841-1.195335 6 6 0 0.295928 0.710841-1.195335 7 1 0-0.175300 1.244736 2.210997 8 1 0 0.011871 2.513023 0.116008 9 1 0-0.011871-2.513023 0.116008 10 1 0 0.109572-1.284680-2.036933 11 1 0-1.385629-0.656887-1.361763 12 1 0 1.385629 0.656887-1.361763 17
13 1 0-0.109572 1.284680-2.036933 14 1 0 0.175300-1.244736 2.210997 NBD E = -271.9793191214 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0 0.228902-1.330534 0.667946 2 6 0 0.228902-1.330534-0.667946 3 6 0-1.107434 0.772240 0.667991 4 6 0-1.107434 0.772240-0.667991 5 1 0 0.178452-2.181102 1.338757 6 1 0 0.178452-2.181102-1.338757 7 1 0-1.898664 1.088289 1.338893 8 1 0-1.898664 1.088289-1.338893 9 6 0 0.228902 0.145383-1.122658 10 6 0 0.228902 0.145383 1.122658 11 6 0 1.143778 0.726880 0.000000 12 1 0 0.516279 0.328036-2.160172 13 1 0 0.516279 0.328036 2.160172 14 1 0 1.187580 1.821184 0.000000 15 1 0 2.153191 0.302023 0.000000 18
CD E = -312.0304 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 6 0-1.214953-1.235561-0.495714 2 1 0-1.821379-1.840339-1.172320 3 6 0 0.008312-1.703874-0.219332 4 1 0 0.292448-2.633063-0.714504 5 6 0-1.923535 0.010217-0.022619 6 1 0-2.428331 0.454393-0.893446 7 1 0-2.739284-0.285137 0.657198 8 6 0 1.082801-1.107614 0.665290 9 1 0 0.665000-0.725111 1.599942 10 1 0 1.770867-1.910197 0.959177 11 6 0-0.008187 1.703931-0.219413 12 1 0-0.291844 2.633402-0.714319 13 6 0 1.215103 1.235509-0.495522 14 1 0 1.821869 1.840515-1.171631 15 6 0-1.083014 1.107810 0.664904 16 1 0-1.771302 1.910430 0.958188 17 1 0-0.665457 0.725879 1.599917 18 6 0 1.923481-0.010503-0.022741 19 1 0 2.739746 0.284715 0.656511 20 1 0 2.427615-0.454970-0.893825 19
CH 3 CN E = -132.7549278 Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): 1 7 0-1.440850 0.000153-0.000304 2 6 0-0.280510-0.000356 0.000722 3 6 0 1.180951 0.000076-0.000151 4 1 0 1.560908-0.824327-0.611872 5 1 0 1.561941-0.117069 1.019332 6 1 0 1.560457 0.942004-0.408754 20
S-6. Spectra of All Products Me Me Me 3ab 21
Me Me Me 3ab 22
S 3ac 23
S 3ac 24
3ad 25
3ad 26
S 3ae 27
S 3ae 28
S 3ae 29
S 3ae' 30
S 3ae' 31
S 3ae' 32
Br N H 3ag 33
Br N H 3ag 34
N 3bh 35
N 3bh 36
N 3bh 37
Me Me Me 3ca 38
Me Me Me 3ca 39
Me Me Me 3ca 40
Ph N H 3cf 41
Ph N H 3cf 42
H Br Me Me 3db 43
H Br Me Me 3db 44
H Br Me Me 3db 45
Ph Ph N H 3ef 46
Ph Ph N H 3ef 47
HN 3kf 48
HN 3kf 49
H H Me Me 3la Me 50
H H Me Me 3la Me 51
CMe 3ai 52
CMe 3ai 53
CMe 3ai 54
Ph 3bk 55
Ph 3bk 56
Ph Ph 3bl 57
Ph Ph 3bl 58
Ph Ph 3jj 59
Ph Ph 3jj 60
Ph Ph 3kl 61
Ph Ph 3kl 62
S 3cp 63
S 3cp 64
S 3cp 65
S Ph 3ep Ph 66
S Ph 3ep Ph 67
H S Br 3fq Ph 68
H S Br 3fq Ph 69
H S Br 3fq Ph 70
H S 3go Me 71
H S 3go Me 72
H S 3go Me 73
(CH 2 ) 7 H 3 C S 3gn Me 74
(CH 2 ) 7 H 3 C S 3gn Me 75
(CH 2 ) 7 H 3 C S 3gn Me 76
Me S Cl 3hr 77
Me S Cl 3hr 78
S Me 3im Me 79
S Me 3im Me 80
H S Ph 3jo Ph 81
H S Ph 3jo Ph 82
H S Ph 3jo Ph 83
H N 2 N 3au 84
H N 2 N 3au 85
H N Cl 3av 86
87
N 3aw 88
N 3aw 89
N 3ax 90
N 3ax 91
H N Me 3bt 92
H N Me 3bt 93
H N Me 3bt 94
H N 3cs Ph 95
H N 3cs Ph 96
H N 3ks 97
H N 3ks 98
3ay 99
3ay 100
3az 101
3az 102
S Ph H H 4a Ph 103
S Ph H H 4a Ph 104
S Ph H H 4a Ph 105
S Ph 5a Ph 106
S Ph 5a Ph 107
S Ph 5a Ph 108
S Ph H H 4b Me 109
S Ph H H 4b Me 110
S Ph H H 4b Me 111
S Ph 5b Me 112
S Ph 5b Me 113
S Ph 5b Me 114