Supporting Information

Solvent-free Microwave-assisted Peroxidative Oxidation of Alcohols Catalyzed by Iron(III)-TEMPO Catalytic Systems

Anirban Karmakar,*a Luísa M.D.R.S. Martins,*a,b M. Fátima C. Guedes da Silva,*a Susanta Hazraa and Armando J. L. Pombeiro*a

aCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001, Lisbon, Portugal. E-mail: , ,

bChemical Engineering Department, ISEL, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal. E-mail:

Figure S1: FT-IR spectra of catalyst 3 before (red line) and after (blue line) the oxidation reaction.

Crystal structure determinations

X-ray quality single crystals of the compounds were immersed in cryo-oil, mounted in a nylon loop and measured at room temperature (1-3). Intensity data were collected using a Bruker APEX-II PHOTON 100 diffractometer with graphite monochromated Mo-Kα (λ 0.71069) radiation. Data were collected using phi and omega scans of 0.5° per frame and a full sphere of data was obtained. Cell parameters were retrieved using Bruker SMART1 software and refined using Bruker SAINT1a on all the observed reflections. Absorption corrections were applied using SADABS1a. Structures were solved by direct methods by using the SHELXS-97 package1b and refined with SHELXL-971b. Calculations were performed using the WinGX System–Version 1.80.031c. The hydrogen atoms attached to carbon atoms and to the nitrogen atoms were inserted at geometrically calculated positions and included in the refinement using the riding-model approximation; Uiso(H) were defined as 1.2Ueq of the parent nitrogen atoms or the carbon atoms for phenyl and methylene residues, and 1.5Ueq of the parent carbon atoms for the methyl groups. Least square refinements with anisotropic thermal motion parameters for all the non-hydrogen atoms and isotropic ones for the remaining atoms were employed.

Compounds 2 contained disordered noncoordinated DMF molecules which could not be modelled reliably. PLATON/SQUEEZE29d was used to correct the data and potential volume of 333 Å3 was found with 88 electrons per unit cell worth of scattering. The electron count suggests the presence of ca. one DMF molecule per asymmetric unit. Elemental analytical data also support this result. These were removed from the model and not included in the empirical formula. Crystallographic data are summarized in Table S3 (Supplementary Information file) and selected bond distances and angles are presented in Table S1. CCDC 1057737-1057739 for respectively, contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

1. (a) Bruker, APEX2 & SAINT, AXS Inc., Madison, WI, 2004; (b) G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr., 2008, 64, 112-122; (c) L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837-838. (d) A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, C34.

Table S1: Selected bond distances (Å) and angles (°) for compounds 1-3
1
Bond distances / Bond angles / Bond angles
Fe1-O1 / 1.9745(18) / <O1-Fe1-O3 / 157.95(8) / <N1-Fe1-Cl2 / 89.88(6)
Fe1-O3 / 1.9822(18) / <O1-Fe1-N1 / 76.29(8) / <N4-Fe1-Cl2 / 168.02(6)
Fe1-N1 / 2.206(2) / <O3-Fe1-N1 / 88.95(8) / <O1-Fe1-Cl1 / 92.98(6)
Fe1-N4 / 2.231(2) / <O1-Fe1-N4 / 87.10(8) / <O3-Fe1-Cl1 / 99.76(6)
Fe1-Cl2 / 2.2898(8) / <O3-Fe1-N4 / 75.60(8) / <N1-Fe1-Cl1 / 168.09(6)
Fe1-Cl1 / 2.2919(8) / <N1-Fe1-N4 / 86.57(8) / <N4-Fe1-Cl1 / 87.75(6)
<O1-Fe1-Cl2 / 103.19(6) / <Cl2-Fe1-Cl1 / 97.70(3)
<O3-Fe1-Cl2 / 92.91(6)
2
Fe1-O1 / 1.9595(15) / <O1-Fe1-O3 / 156.27(6) / <O1-Fe1-N1 / 77.04(6)
Fe1-O3 / 2.0076(15) / <O3-Fe1-N1 / 86.24(7) / <O1-Fe1-Cl1 / 102.83(5)
Fe1-N1 / 2.2054(18) / <O3-Fe1-Cl1 / 93.87(5) / <N1-Fe1-Cl1 / 90.32(5)
Fe1-Cl1 / 2.2553(7) / <O1-Fe1-N4 / 86.20(7) / <O3-Fe1-N4 / 75.04(6)
Fe1-N4 / 2.2711(18) / <N1-Fe1-N4 / 83.08(7) / <Cl1-Fe1-N4 / 167.38(5)
Fe1-Cl2 / 2.2964(7) / <O1-Fe1-Cl2 / 94.82(5) / <O3-Fe1-Cl2 / 98.83(5)
<N1-Fe1-Cl2 / 168.21(5) / <Cl1-Fe1-Cl2 / 99.90(3)
3
Fe1-O1 / 1.9555(14) / <O1-Fe1-N5 / 88.11(6) / <O1-Fe1-N1 / 76.40(6)
Fe1-N5 / 2.1607(17) / <O1-Fe1-N4 / 157.47(6) / <N5-Fe1-N1 / 84.17(6)
Fe1-N4 / 2.1641(17) / <N5-Fe1-N4 / 74.60(6) / <N4-Fe1-N1 / 87.38(6)
Fe1-Cl1 / 2.2504(6) / <O1-Fe1-Cl1 / 97.14(5) / <Cl1-Fe1-N1 / 172.81(4)
Fe1-N1 / 2.2557(16) / <N5-Fe1-Cl1 / 92.54(5) / <O1-Fe1-Cl2 / 100.47(5)
Fe1-Cl2 / 2.3094(6) / <N4-Fe1-Cl1 / 97.93(5) / <N5-Fe1-Cl2 / 165.33(5)
<N4-Fe1-Cl2 / 93.87(5) / <Cl1-Fe1-Cl2 / 98.12(2)
<N1-Fe1-Cl2 / 86.30(4)
Table S2: Hydrogen bond geometry (Å, °) in compounds 1-3
Compound / D-H---A / D-H (Å) / H∙∙∙A (Å) / D∙∙∙A (Å) / <D−H∙∙∙A(°) / Symmetry
1 / N6-H6B····O4 / 0.88 / 2.07 / 2.726(4) / 131.0 / -
N3-H3A····O2 / 0.84 / 2.16 / 2.749(5) / 127.0 / -
N3-H3B····Cl2 / 0.80 / 2.94 / 3.392(3) / 118.0 / -x+1, -y+1, -z+1
N6-H6A····N5 / 0.77 / 2.38 / 3.113(4) / 159.0 / -x, -y+1, -z
C12-H12A····O3 / 0.97 / 1.86 / 2.787(3) / 158.6 / x+1, y, z
C12-H12A····O4 / 0.97 / 2.51 / 3.106(3) / 119.9 / x+1, y, z
C12-H12B····Cl1 / 0.97 / 2.65 / 3.438(3) / 138.3 / -
C5-H5····O2 / 0.93 / 2.54 / 3.422(4) / 159.0 / x-1, y, z
O5-H5B····Cl2 / 0.98 / 2.83 / 3.684(5) / 146.1 / x+1, y, z
C12-H12B····O1 / 0.97 / 2.07 / 2.822(3) / 133.4 / -
2 / N6-H6A····N5 / 0.83 / 2.24 / 3.070(3) / 177.0 / -x+1, -y+1, -z+2
N6-H6B····O4 / 0.82 / 2.18 / 2.769(3) / 129.0 / -
N3-H3A····N2 / 0.76 / 2.29 / 3.044(3) / 171.0 / -x, -y+1, -z+1
N3-H3B····O2 / 0.81 / 2.16 / 2.758(3) / 131 / -
N3-H3B····O2 / 0.81 / 2.53 / 3.037(4) / 122.0 / -x+1, -y+1, -z+1
N7-H7N····O3 / 0.96 / 2.60 / 3.199(3) / 120.7 / x, y-1, z
N7-H7N····O4 / 0.96 / 1.71 / 2.666(2) / 176.9 / x, y-1, z
C4-H4····O1 / 0.93 / 2.53 / 3.422(3) / 161.6 / x-1, y, z
C9-H9····Cl1 / 0.93 / 2.86 / 3.540(2) / 130.7 / x, y-1, z
C11-H11····Cl2 / 0.93 / 2.86 / 3.674(3) / 147.5 / -x+1, -y+1, -z+2
C15-H15····O3 / 0.93 / 2.50 / 3.144(3) / 126.1 / x, y-1, z
3 / N3-H3A····Cl2 / 0.84 / 2.63 / 3.428(2) / 160.0 / -x+2, -y+1, -z
N3-H3B····O2 / 0.85 / 2.10 / 2.741(3) / 132.0 / -
C6-H6····Cl2 / 0.93 / 2.72 / 3.324(2) / 123.1 / -
C15-H15····O1 / 0.93 / 2.48 / 2.991(3) / 114.4 / -
C14-H14····Cl2 / 0.93 / 2.94 / 3.618(3) / 131.0 / x-1/2, -y+1/2, z+1/2
C12-H12····N2 / 0.93 / 2.48 / 3.394(3) / 166.3 / -x+5/2, y-1/2, -z+1/2
Table S3: Crystal data and structure refinement details for 1-3
Identification name / 1 / 2 / 3
Formulae / C12H15Cl2FeN6O5 / C15H13Cl2FeN7O4 / C15H12Cl2FeN5O2
Mol. wt. / 450.05 / 482.07 / 421.05
Crystal system / Monoclinic / Triclinic / Monoclinic
Space group / P21/n / P-1 / P21/n
Temperature /K / 296 / 296 / 296
Wavelength /Å / 0.71073 / 0.71073 / 0.71073
a /Å / 7.9691(7) / 8.0949(5) / 8.4059(3)
b /Å / 13.0747(13) / 9.6052(6) / 16.6535(7)
c /Å / 17.7776(19) / 16.1597(10) / 12.3067(5)
α/° / 90 / 102.974(3) / 90
β/° / 94.836(4) / 94.223(2) / 103.664(2)
γ/° / 90 / 96.067(3) / 90
V/ Å3 / 1845.7(3) / 1211.37(13) / 1674.03(12)
Z / 4 / 2 / 4
Density/Mgm-3 / 1.620 / 1.322 / 1.671
Abs. Coeff. /mm-1 / 1.143 / 0.874 / 1.240
F(000) / 916 / 488 / 852
Refl. collected / 23117 / 15384 / 28892
Refl. unique / 3765 / 4429 / 3434
Max. 2θ/° / 26.372 / 25.382 / 26.365
Rint / 0.0270 / 0.0226 / 0.0382
Ranges (h, k, l) / -9<= h <=9
-16<= k <=16
-22<= l <= 22 / -9 <= h <=9
-11<= k <=11
-19<= l <= 19 / -10<= h <= 10
-20 <= k <=20
-15<= l <=15
Complete to 2θ (%) / 99.9 / 99.2 / 100
Refl. with I > 2σ(I) / 3214 / 3740 / 2842
Data/ Restraints/Parameters / 3765 /0 / 252 / 4429/0/274 / 3434/ 0/ 232
Goof (F2) / 1.068 / 1.107 / 1.112
R1 [I > 2s(I)] / 0.0475 / 0.0386 / 0.0311
wR2 [I > 2s(I)] / 0.1234 / 0.0983 / 0.0741
R1 [all data] / 0.0543 / 0.0460 / 0.0417
wR2 [all data] / 0.1287 / 0.1032 / 0.0796