Synthesis, Characterization and Reactivities of Molybdenum and Tungsten PONOP Pincer Complexes

Transcription

1 Synthesis, Characterization and Reactivities of Molybdenum and Tungsten PONOP Pincer Complexes Ruth Castro-Rodrigo, Sumit Chakraborty, Lloyd Munjanja, William W. Brennessel, and William D. Jones* Department of Chemistry, University of Rochester, Rochester, New York 14627, United States. Table of Contents: Characterization data for the Complexes 2a d, 3a - d (NMR and IR) S1 S29 13 CO incorporation experiments S30 NMR spectra for the 1-hexene isomerization experiments NMR data, kinetic plot, and GC data for the isomerization of allylbenzene NMR and GC data for the isomerization of 1-octene Variable Temperature 1 H NMR of complex 3d Simulation of hydride resonance for complex 3b. Eyring plot for hydride fluxionality in complex 3b. Crystal Data and Refinement Parameters for 2a-d. Selected bond lengths (Å) and angles (deg) for 2a-d. X-ray Characterization data for the Complexes 2a - d S31 S32 S33 S34 S35 S36 S37 S38 S39 S40 S41 S42-S91 S-1

2 Characterization for Complex 2a [( t BuPONOP)Mo(CO) 3 Figure S1 1 H NMR of 2a C 6 D 6 at RT S-2

3 Figure S2 31 P{ 1 H} NMR C 6 D 6 at RT for 2a S-3

4 Figure S3 13 C{ 1 H} NMR of 2a C 6 D 6 at RT S-4

5 Characterization for Complex 2b [( i PrPONOP)Mo(CO) 3 Figure S4 1 H NMR of 2b C 6 D 6 at RT S-5

6 Figure S5 31 P{ 1 H} NMR C 6 D 6 at RT for 2b S-6

7 Figure S6 13 C{ 1 H} NMR of 2b C 6 D 6 at RT S-7

8 Characterization for Complex 2c [( t BuPONOP)W (CO) 3 Figure S7 1 H NMR of 2c C 6 D 6 at RT S-8

9 Figure S8 31 P{ 1 H} NMR C 6 D 6 at RT for 2c S-9

10 Figure S9 13 C{ 1 H} NMR of 2c C 6 D 6 at RT S-10

11 Characterization for Complex 2d [( i PrPONOP)W(CO) 3 Figure S10 1 H NMR of 2d C 6 D 6 at RT S-11

12 Figure S11 31 P{ 1 H} NMR C 6 D 6 at RT for 2d S-12

13 Figure S12 13 C{ 1 H} NMR of 2d C 6 D 6 at RT S-13

14 Characterization for Complex 3a [( t BuPONOP)Mo(CO) 3 H]BF 4 Figure S13 1 H NMR of 3a, CD 2 Cl 2 at RT S-14

15 Figure S14 31 P{ 1 H} NMR, CD 2 Cl 2 at RT for 3a S-15

16 Figure S15 13 C{ 1 H} NMR of 3a, CD 2 Cl 2 at RT S-16

17 Figure S16 Solid IR for for 3a S-17

18 Characterization for Complex 3b [( i PrPONOP)Mo(CO) 3 H]BF 4 Figure S17 1 H NMR of 3b, CD 2 Cl 2 at RT S-18

19 Figure S18 31 P{ 1 H} NMR, CD 2 Cl 2 at -80 o C for 3b S-19

20 Figure S19 13 C{ 1 H} NMR of 3b, CD 2 Cl 2 at RT S-20

21 Figure S20 Solid IR for for 3b S-21

22 Characterization for Complex 3c [( t BuPONOP)W(CO) 3 H]BF 4 Figure S21 1 H NMR of 3c, CD 2 Cl 2 at RT S-22

23 Figure S22 13 C{ 1 H} NMR of 3c, CD 2 Cl 2 at RT S-23

24 Figure S23 31 P{ 1 H} NMR, CD 2 Cl 2 at RT for 3c S-24

25 Figure S24 Solid IR for for 3c S-25

26 Characterization for Complex 3d [( i PrPONOP)W(CO) 3 H]BF 4 Figure S25 1 H NMR of 3d, CD 2 Cl 2 at RT S-26

27 Figure S26 13 C{ 1 H} NMR of 3d, CD 2 Cl 2 at RT S-27

28 Figure S27 31 P{ 1 H} NMR, CD 2 Cl 2 at RT for 3d S-28

29 Figure S28 Solid IR for for 3d S-29

30 Mo- 13 CO cis Mo- 13 CO N-trans? Dissolved free 13 CO Figure S29: 13 CO incorporation in the 3b complex during reaction S-30

31 Isomerization of 1-hexene with 10 mol% of 3b. Conditions: [3b] = 32 mm, [1-hexene] = 328 mm, [internal standard- 1, 4 dibromobenzene] = 328 mm, 0.5 ml of CD 2 Cl 2, 9 h at 65 o C S-31

32 H H 3 C H 3 C H H H H 3 C H CH 3 Figure S30 (top) 1 H NMR in CD 2 Cl 2 showing reaction mixture at t= 0 hr and t = 9 hr (b) 1 H NMR spectra showing major isomer products after 9 h. S-32

33 Figure S H NMR spectra of the catalytic isomerization of allylbenzene (A) to trans- methylstyrene (B) and cis- -methylstyrene (C) by [( ipr PONOP)Mo(CO) 3 H] + BF 4, 3b, in CD 2 Cl 2 at 65 C. S = solvent residual protons. [allylbenzene] = 0.29 M. 7% catalyst loading slope = (3) h -1 ln %SM t, h Figure S-32. First order plot for the isomerization of allylbenzene to -methylstyrene using 1 H NMR data for Me resonances. S-33

34 (a) (b) (c) Figure S-33. GC traces of the catalytic isomerization of allylbenzene (A) to trans- methylstyrene (B) and cis- -methylstyrene by [( ipr PONOP)Mo(CO) 3 H] + BF 4, 3b, in CD 2 Cl 2 at 65 C. [allylbenzene] = 0.29 M. 7% catalyst loading. (a) allylbenzene in CH 2 Cl 2, (b) trans- allylbenzene (Aldrich) in CH 2 Cl 2, (c) reaction mixture in CD 2 Cl 2. Shimadzu GC-2010 with Agilent GS-GASPRO PLOT column (30m x 0.32 mm ID), /min, column flow: 2 ml/min, 25:1 split. S-34

35 Figure S H NMR spectra of the catalytic isomerization of 1-octene to internal octenes by [( ipr PONOP)Mo(CO) 3 H] + BF 4, 3b, in CD 2 Cl 2 at 65 C. [1-octene] = 0.22 M. 7% catalyst loading. A = 1-octene vinyl resonances; B = internal octane vinyl resonances; S = residual solvent resonances. S-35

36 (a) (b) Figure S-35. GC traces of the catalytic isomerization of 1-octene to internal octenes by [( ipr PONOP)Mo(CO) 3 H] + BF 4, 3b, in CD 2 Cl 2 at 65 C. [1-octene] = 0.22 M. 7% catalyst loading. (a) after 4.7 hrs, (b) after 40.7 hrs. Shimadzu GC-2010 with Agilent GS-GASPRO PLOT column (30m x 0.32 mm ID), /min, column flow: 2 ml/min, 25:1 split. S-36

37 CO O P( i BF Pr 2 ) 4 N W CO H O P CO ( i Pr 2 ) 3d 51.5 o C 29.9 o C 18.9 o C 14.0 o C o C o C o C o C o C Figure S36. Variable Temperature 1 H NMR spectra in CD 2 Cl 2 of complex 3d S-37

38 Figure S-37. Simulation of hydride resonance for complex 3b, overlaid on actual spectra. 243 K 283 K [c: nuts data 2nuts] ( , 16:53:54) [c: nuts data 6nuts] ( , 16:58:14) 2nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = 0.10 Wa = nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = Wa = ppm 253 K 293 K ppm 3nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = 1.00 Wa = 3.00 [c: nuts data 3nuts] ( , 16:55:08) 7nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = Wa = 4.00 [c: nuts data 7nuts] ( , 16:59:04) 263 K ppm ppm 303 K 4nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = 6.00 Wa = 2.80 [c: nuts data 4nuts] ( , 16:56:32) 8nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = Wa = 5.30 [c: nuts data 8nuts] ( , 16:59:45) ppm 273 K 313 K ppm 5nuts Vab = Vx = Jab = Jax = Jbx = Right-Hz = WdthHz = kab = Wa = 3.00 [c: nuts data 5nuts] ( , 16:57:15) 9nuts Vab = Vx = Jab = 0.00 Jax = Jbx = Right-Hz = WdthHz = kab = Wa = 8.80 [c: nuts data 9nuts] ( , 17:00:18) ppm ppm S-38

39 Figure S-38. Eyring plot for hydride fluxionality in complex 3b ln(k/t) /T 95% confidence limits: H = ± 0.62 kcal/mol S = 22.2 ± 2.2 e.u. G = 14.0 ± K S-39

40 Table S-1. Crystal Data and Refinement Parameters for 2a-d. 2a 2b 2c 2d cryst syst monoclinic monoclinic monoclinic orthorhombic space group P2 1 /n P2 1 /n P2 1 /n P a, Å (5) (3) (16) (19) b, Å (4) (3) (14) (2) c, Å (5) (5) (16) (4), deg , deg (6) (4) (19) 90, deg Volume, Å (15) (10) (5) (7) Z no. of data collected R 1, wr 2 (I > 2 (I)) R 1, wr 2 (all data) 0.030, , , , , , , , S-40

41 Table S-2. Selected bond lengths (Å) and angles (deg). 2a (M=Mo, R= t Bu) 2b (M=Mo), R= i Pr) 2c (M=W), R= t Bu) 2d (M=W), R= i Pr M(1) C(22)/C(1) (14) 1.961(5) (17) 1.969(2) M(1) C(23)/C(2) (13) 2.029(5) (17) 2.019(2) M(1) C(24)/C(3) (14) 1.997(5) (18) 2.016(2) M(1) P(1) (8) (13) (5) (6) M(1) P(2) (8) (14) (5) (6) M(1) N(1) (12) 2.241(9) (13) (17) P(1) M(1) P(2) (16) (4) (14) (2) N(1) M(1) P(1) 75.55(2) 76.42(10) 75.58(3) 76.57(5) N(1) M(1) P(2) 75.50(2) 76.54(10) 75.52(3) 76.17(5) N(1) M(1) C(22)/C(1) 90.18(4) (18) 91.11(6) (8) N(1) M(1) C(23)/C(2) (4) 93.94(17) (6) 97.42(8) N(1) M(1) C(24)/C(3) (4) 99.86(18) (6) 96.43(7) C(22)/C(2) M(1) C(24)/C(3) (5) 166.1(2) (7) (9) S-41

42 REFERENCE NUMBER: jonrcr01 (2a) CRYSTAL STRUCTURE REPORT C 24 H 39 Mo N O 5 P 2 Report prepared for: Dr. R. Castro-Rodrigo, Prof. W. Jones October 15, 2013 Ruth Castro-Rodrigo X-ray Crystallographic Facility Department of Chemistry, University of Rochester 120 Trustee Road Rochester, NY S-42

43 Data collection A crystal (0.300 x x mm 3 ) was placed onto the tip of a 0.1 mm diameter glass capillary tube or fiber and mounted on a Bruker SMART APEX II CCD platform diffractometer for a data collection at 100.0(5) K. 1 A preliminary set of cell constants and an orientation matrix were calculated from reflections harvested from three orthogonal wedges of reciprocal space. The full data collection was carried out using MoK radiation (graphite monochromator) with a frame time of 15 seconds and a detector distance of 4.02 cm. A randomly oriented region of reciprocal space was surveyed: six major sections of frames were collected with 0.50º steps in at six different settings and a detector position of -38º in 2. The intensity data were corrected for absorption. 2 Final cell constants were calculated from the xyz centroids of 3765 strong reflections from the actual data collection after integration. 3 See Table S1 for additional crystal and refinement information. Structure solution and refinement The structure was solved using SHELXS and refined using SHELXL The space group P2 1 /n was determined based on systematic absences. A direct-methods solution was calculated which provided most nonhydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. The final full matrix least squares refinement converged to R1 = (F 2, I > 2 (I)) and wr2 = (F 2, all data). Structure description The structure is the one suggested. The asymmetric unit contains one molybdenum molecule in a general position. Unless noted otherwise all structural diagrams containing thermal displacement ellipsoids are drawn at the 50 % probability level. Data collection, structure solution, and structure refinement were conducted at the X-ray Crystallographic Facility, B51 Hutchison Hall, Department of Chemistry, University of Rochester. All publications arising from this report MUST either 1) include Ruth Castro-Rodrigo as a coauthor or 2) acknowledge Ruth Castro-Rodrigo and the X-ray Crystallographic Facility of the Department of Chemistry at the University of Rochester. S-43

44 1 APEX2, version ; Bruker AXS: Madison, WI, Sheldrick, G. M. SADABS, version 2012/1; University of Göttingen: Göttingen, Germany, SAINT, version 8.27B; Bruker AXS: Madison, WI, Sheldrick, G. M. SHELXS-2013/1; University of Göttingen: Göttingen, Germany, Sheldrick, G. M. SHELXL-2013/4; University of Göttingen: Göttingen, Germany, Some equations of interest: R int = F 2 o -< F 2 o > / F 2 o R1 = F o - F c / F o wr2 = [ [w(f o2 -F 2 c ) 2 ] / [w(f 2 o ) 2 ]] 1/2 where w = 1 / [ 2 (F o2 ) + (ap ) 2 + bp] and P = 1/3 max (0, F o2 ) + 2/3 F 2 c GOF = S = [ [w(f o2 -F 2 c ) 2 ] / (m-n )] 1/2 where m = number of reflections and n = number of parameters S-44

45 Table S-3. Crystal data and structure refinement for jonrcr01. (2a) Identification code jonrcr01 Empirical formula C 24 H 39 Mo N O 5 P 2 Formula weight Temperature 100.0(5) K Wavelength Å Crystal system monoclinic Space group P2 1 /n Unit cell dimensions a = (5) Å = 90 b = (4) Å = (6) c = (5) Å = 90 Volume (15) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1208 Crystal color, morphology yellow, block Crystal size x x mm 3 Theta range for data collection to Index ranges -26 h 26, -23 k 22, -27 l 27 Reflections collected Independent reflections [R(int) = ] Observed reflections Completeness to theta = % Absorption correction Multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 310 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S-45

46 Table S-4. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for jonrcr01 (2a). U eq is defined as one third of the trace of the orthogonalized U ij tensor. x y z U eq Mo1 9116(1) 8897(1) 1887(1) 10(1) P1 9604(1) 7085(1) 2194(1) 12(1) P2 9595(1) 10692(1) 1979(1) 11(1) O (1) 7097(1) 2237(1) 14(1) O (1) 10617(1) 1992(1) 13(1) O3 8284(1) 8752(1) -396(1) 23(1) O4 6810(1) 9008(1) 1344(1) 24(1) O5 8964(1) 9059(1) 3836(1) 28(1) N (1) 8864(1) 2189(1) 11(1) C (1) 7979(1) 2330(1) 12(1) C (1) 7927(1) 2560(1) 15(1) C (1) 8833(1) 2601(1) 16(1) C (1) 9750(1) 2404(1) 14(1) C (1) 9728(1) 2200(1) 11(1) C6 8981(1) 11646(1) 959(1) 17(1) C7 8151(1) 12228(1) 1090(1) 31(1) C8 8468(2) 11078(1) 4(1) 35(1) C9 9732(1) 12399(1) 889(1) 24(1) C (1) 11386(1) 3176(1) 16(1) C (1) 10720(1) 3948(1) 21(1) C (1) 11490(1) 3425(1) 25(1) C (1) 12438(1) 3236(1) 23(1) C (1) 6019(1) 1288(1) 15(1) C (1) 6468(1) 265(1) 24(1) C (1) 5540(1) 1423(1) 28(1) C (1) 5200(1) 1348(1) 24(1) C (1) 6561(1) 3459(1) 17(1) C (1) 7294(1) 4155(1) 21(1) C (1) 6551(1) 3692(1) 24(1) C (1) 5496(1) 3659(1) 24(1) C (1) 8801(1) 443(1) 14(1) C (1) 8954(1) 1525(1) 15(1) C (1) 8997(1) 3180(1) 17(1) S-46

47 Table S-5. Bond lengths [Å] and angles [ ] for jonrcr01 (2a). Mo(1)-C(23) (13) C(9)-H(9B) Mo(1)-C(24) (14) C(9)-H(9C) Mo(1)-C(22) (14) C(10)-C(13) (18) Mo(1)-N(1) (12) C(10)-C(12) (18) Mo(1)-P(2) (8) C(10)-C(11) (19) Mo(1)-P(1) (8) C(11)-H(11A) P(1)-O(1) (10) C(11)-H(11B) P(1)-C(14) (13) C(11)-H(11C) P(1)-C(18) (14) C(12)-H(12A) P(2)-O(2) (10) C(12)-H(12B) P(2)-C(6) (13) C(12)-H(12C) P(2)-C(10) (13) C(13)-H(13A) O(1)-C(1) (14) C(13)-H(13B) O(2)-C(5) (14) C(13)-H(13C) O(3)-C(22) (15) C(14)-C(15) (19) O(4)-C(23) (15) C(14)-C(16) (18) O(5)-C(24) (16) C(14)-C(17) (17) N(1)-C(5) (14) C(15)-H(15A) N(1)-C(1) (14) C(15)-H(15B) C(1)-C(2) (15) C(15)-H(15C) C(2)-C(3) (16) C(16)-H(16A) C(2)-H(2A) C(16)-H(16B) C(3)-C(4) (16) C(16)-H(16C) C(3)-H(3A) C(17)-H(17A) C(4)-C(5) (15) C(17)-H(17B) C(4)-H(4A) C(17)-H(17C) C(6)-C(8) 1.512(2) C(18)-C(21) (18) C(6)-C(9) (18) C(18)-C(20) (19) C(6)-C(7) 1.544(2) C(18)-C(19) (18) C(7)-H(7A) C(19)-H(19A) C(7)-H(7B) C(19)-H(19B) C(7)-H(7C) C(19)-H(19C) C(8)-H(8A) C(20)-H(20A) C(8)-H(8B) C(20)-H(20B) C(8)-H(8C) C(20)-H(20C) C(9)-H(9A) C(21)-H(21A) S-47

48 C(21)-H(21B) C(21)-H(21C) C(23)-Mo(1)-C(24) 77.04(5) C(23)-Mo(1)-C(22) 85.84(5) C(24)-Mo(1)-C(22) (5) C(23)-Mo(1)-N(1) (4) C(24)-Mo(1)-N(1) (4) C(22)-Mo(1)-N(1) 90.18(4) C(23)-Mo(1)-P(2) (3) C(24)-Mo(1)-P(2) 90.76(4) C(22)-Mo(1)-P(2) 93.62(3) N(1)-Mo(1)-P(2) 75.50(2) C(23)-Mo(1)-P(1) (3) C(24)-Mo(1)-P(1) 90.29(3) C(22)-Mo(1)-P(1) 94.11(3) N(1)-Mo(1)-P(1) 75.55(2) P(2)-Mo(1)-P(1) (16) O(1)-P(1)-C(14) 97.76(5) O(1)-P(1)-C(18) 97.07(5) C(14)-P(1)-C(18) (6) O(1)-P(1)-Mo(1) (3) C(14)-P(1)-Mo(1) (4) C(18)-P(1)-Mo(1) (4) O(2)-P(2)-C(6) 97.80(5) O(2)-P(2)-C(10) 97.01(5) C(6)-P(2)-C(10) (6) O(2)-P(2)-Mo(1) (3) C(6)-P(2)-Mo(1) (4) C(10)-P(2)-Mo(1) (4) C(1)-O(1)-P(1) (7) C(5)-O(2)-P(2) (7) C(5)-N(1)-C(1) (9) C(5)-N(1)-Mo(1) (7) C(1)-N(1)-Mo(1) (7) O(1)-C(1)-N(1) (9) O(1)-C(1)-C(2) (9) N(1)-C(1)-C(2) (10) C(3)-C(2)-C(1) (10) C(3)-C(2)-H(2A) C(1)-C(2)-H(2A) C(4)-C(3)-C(2) (10) C(4)-C(3)-H(3A) C(2)-C(3)-H(3A) C(3)-C(4)-C(5) (10) C(3)-C(4)-H(4A) C(5)-C(4)-H(4A) O(2)-C(5)-N(1) (9) O(2)-C(5)-C(4) (9) N(1)-C(5)-C(4) (10) C(8)-C(6)-C(9) (12) C(8)-C(6)-C(7) (13) C(9)-C(6)-C(7) (12) C(8)-C(6)-P(2) (9) C(9)-C(6)-P(2) (9) C(7)-C(6)-P(2) (9) C(6)-C(7)-H(7A) C(6)-C(7)-H(7B) H(7A)-C(7)-H(7B) C(6)-C(7)-H(7C) H(7A)-C(7)-H(7C) H(7B)-C(7)-H(7C) C(6)-C(8)-H(8A) C(6)-C(8)-H(8B) H(8A)-C(8)-H(8B) C(6)-C(8)-H(8C) H(8A)-C(8)-H(8C) H(8B)-C(8)-H(8C) C(6)-C(9)-H(9A) C(6)-C(9)-H(9B) H(9A)-C(9)-H(9B) C(6)-C(9)-H(9C) H(9A)-C(9)-H(9C) H(9B)-C(9)-H(9C) C(13)-C(10)-C(12) (11) C(13)-C(10)-C(11) (11) S-48

49 C(12)-C(10)-C(11) (11) C(14)-C(16)-H(16C) C(13)-C(10)-P(2) (9) H(16A)-C(16)-H(16C) C(12)-C(10)-P(2) (9) H(16B)-C(16)-H(16C) C(11)-C(10)-P(2) (8) C(14)-C(17)-H(17A) C(10)-C(11)-H(11A) C(14)-C(17)-H(17B) C(10)-C(11)-H(11B) H(17A)-C(17)-H(17B) H(11A)-C(11)-H(11B) C(14)-C(17)-H(17C) C(10)-C(11)-H(11C) H(17A)-C(17)-H(17C) H(11A)-C(11)-H(11C) H(17B)-C(17)-H(17C) H(11B)-C(11)-H(11C) C(21)-C(18)-C(20) (11) C(10)-C(12)-H(12A) C(21)-C(18)-C(19) (11) C(10)-C(12)-H(12B) C(20)-C(18)-C(19) (11) H(12A)-C(12)-H(12B) C(21)-C(18)-P(1) (9) C(10)-C(12)-H(12C) C(20)-C(18)-P(1) (9) H(12A)-C(12)-H(12C) C(19)-C(18)-P(1) (8) H(12B)-C(12)-H(12C) C(18)-C(19)-H(19A) C(10)-C(13)-H(13A) C(18)-C(19)-H(19B) C(10)-C(13)-H(13B) H(19A)-C(19)-H(19B) H(13A)-C(13)-H(13B) C(18)-C(19)-H(19C) C(10)-C(13)-H(13C) H(19A)-C(19)-H(19C) H(13A)-C(13)-H(13C) H(19B)-C(19)-H(19C) H(13B)-C(13)-H(13C) C(18)-C(20)-H(20A) C(15)-C(14)-C(16) (11) C(18)-C(20)-H(20B) C(15)-C(14)-C(17) (11) H(20A)-C(20)-H(20B) C(16)-C(14)-C(17) (11) C(18)-C(20)-H(20C) C(15)-C(14)-P(1) (8) H(20A)-C(20)-H(20C) C(16)-C(14)-P(1) (9) H(20B)-C(20)-H(20C) C(17)-C(14)-P(1) (9) C(18)-C(21)-H(21A) C(14)-C(15)-H(15A) C(18)-C(21)-H(21B) C(14)-C(15)-H(15B) H(21A)-C(21)-H(21B) H(15A)-C(15)-H(15B) C(18)-C(21)-H(21C) C(14)-C(15)-H(15C) H(21A)-C(21)-H(21C) H(15A)-C(15)-H(15C) H(21B)-C(21)-H(21C) H(15B)-C(15)-H(15C) O(3)-C(22)-Mo(1) (11) C(14)-C(16)-H(16A) O(4)-C(23)-Mo(1) (11) C(14)-C(16)-H(16B) O(5)-C(24)-Mo(1) (12) H(16A)-C(16)-H(16B) S-49

50 Table S-6. Anisotropic displacement parameters (Å 2 x 10 3 ) for jonrcr01 (2a). The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Mo1 9(1) 9(1) 12(1) 0(1) 5(1) 0(1) P1 10(1) 9(1) 16(1) 1(1) 6(1) 0(1) P2 10(1) 9(1) 13(1) 0(1) 5(1) 0(1) O1 11(1) 9(1) 23(1) 0(1) 9(1) 0(1) O2 11(1) 10(1) 19(1) 1(1) 9(1) 1(1) O3 32(1) 19(1) 15(1) -2(1) 9(1) -1(1) O4 12(1) 28(1) 32(1) -7(1) 10(1) -1(1) O5 43(1) 27(1) 24(1) 2(1) 24(1) 3(1) N1 10(1) 10(1) 13(1) 0(1) 5(1) 0(1) C1 10(1) 11(1) 14(1) 0(1) 6(1) 0(1) C2 10(1) 12(1) 22(1) 1(1) 7(1) 1(1) C3 10(1) 14(1) 23(1) -1(1) 8(1) -1(1) C4 11(1) 12(1) 20(1) 0(1) 8(1) -1(1) C5 11(1) 10(1) 13(1) 0(1) 6(1) 0(1) C6 15(1) 14(1) 18(1) 4(1) 5(1) 1(1) C7 21(1) 28(1) 43(1) 11(1) 14(1) 9(1) C8 50(1) 20(1) 18(1) 3(1) 3(1) -5(1) C9 24(1) 18(1) 29(1) 6(1) 13(1) 1(1) C10 19(1) 16(1) 16(1) -4(1) 10(1) -2(1) C11 23(1) 23(1) 14(1) -2(1) 6(1) -3(1) C12 32(1) 23(1) 32(1) -5(1) 24(1) 1(1) C13 29(1) 16(1) 24(1) -6(1) 11(1) -6(1) C14 14(1) 12(1) 20(1) -2(1) 7(1) -1(1) C15 30(1) 16(1) 20(1) -3(1) 6(1) 0(1) C16 21(1) 23(1) 38(1) -5(1) 14(1) -9(1) C17 22(1) 16(1) 30(1) -4(1) 10(1) 4(1) C18 19(1) 14(1) 18(1) 4(1) 8(1) 1(1) C19 21(1) 18(1) 17(1) 2(1) 4(1) 3(1) C20 30(1) 22(1) 28(1) 3(1) 20(1) -2(1) C21 30(1) 15(1) 24(1) 6(1) 10(1) 5(1) C22 15(1) 12(1) 17(1) -1(1) 8(1) -1(1) C23 14(1) 14(1) 18(1) -2(1) 7(1) 0(1) C24 20(1) 15(1) 17(1) 2(1) 10(1) 2(1) S-50

51 Table S-7. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for jonrcr01 (2a). x y z U(eq) H2A H3A H4A H7A H7B H7C H8A H8B H8C H9A H9B H9C H11A H11B H11C H12A H12B H12C H13A H13B H13C H15A H15B H15C H16A H16B H16C H17A H17B H17C S-51

52 H19A H19B H19C H20A H20B H20C H21A H21B H21C S-52

53 Table S-8. Torsion angles [ ] for jonrcr01 (2a). C14-P1-O1-C (9) O2-P2-C6-C (10) C18-P1-O1-C (9) C10-P2-C6-C (11) Mo1-P1-O1-C (9) Mo1-P2-C6-C (10) C6-P2-O2-C (9) O2-P2-C10-C (10) C10-P2-O2-C (9) C6-P2-C10-C (11) Mo1-P2-O2-C (9) Mo1-P2-C10-C (8) P1-O1-C1-N (14) O2-P2-C10-C (9) P1-O1-C1-C (9) C6-P2-C10-C (10) C5-N1-C1-O (10) Mo1-P2-C10-C (10) Mo1-N1-C1-O1 3.56(14) O2-P2-C10-C (9) C5-N1-C1-C2 5.31(16) C6-P2-C10-C (8) Mo1-N1-C1-C (9) Mo1-P2-C10-C (9) O1-C1-C2-C (11) O1-P1-C14-C (9) N1-C1-C2-C3-2.94(18) C18-P1-C14-C (9) C1-C2-C3-C4-0.92(18) Mo1-P1-C14-C (11) C2-C3-C4-C5 2.10(18) O1-P1-C14-C (9) P2-O2-C5-N (13) C18-P1-C14-C (10) P2-O2-C5-C (8) Mo1-P1-C14-C (10) C1-N1-C5-O (9) O1-P1-C14-C (10) Mo1-N1-C5-O2-2.30(13) C18-P1-C14-C (11) C1-N1-C5-C4-4.00(16) Mo1-P1-C14-C (8) Mo1-N1-C5-C (8) O1-P1-C18-C (10) C3-C4-C5-O (10) C14-P1-C18-C (11) C3-C4-C5-N1 0.41(17) Mo1-P1-C18-C (8) O2-P2-C6-C (11) O1-P1-C18-C (9) C10-P2-C6-C (11) C14-P1-C18-C (10) Mo1-P2-C6-C (13) Mo1-P1-C18-C (10) O2-P2-C6-C (10) O1-P1-C18-C (9) C10-P2-C6-C (11) C14-P1-C18-C (8) Mo1-P2-C6-C (8) Mo1-P1-C18-C (9) S-53

54 REFERENCE NUMBER: jonlm13 (2b) CRYSTAL STRUCTURE REPORT C 20 H 31 Mo N O 5 P 2 or (iprponop)mo(co) 3 Report prepared for: L. Munjanja, Prof. W. Jones November 10, 2014 William W. Brennessel X-ray Crystallographic Facility Department of Chemistry, University of Rochester 120 Trustee Road Rochester, NY S-54

55 Data collection A crystal (0.18 x 0.14 x 0.05 mm 3 ) was placed onto the tip of a thin glass optical fiber and mounted on a Bruker SMART APEX II CCD platform diffractometer for a data collection at 100.0(5) K. 1 A preliminary set of cell constants and an orientation matrix were calculated from reflections harvested from three orthogonal wedges of reciprocal space. The full data collection was carried out using MoK radiation (graphite monochromator) with a frame time of 60 seconds and a detector distance of 4.02 cm. A randomly oriented region of reciprocal space was surveyed: five major sections of frames were collected with 0.50º steps in at five different settings and a detector position of -38º in 2. The intensity data were corrected for absorption. 2 Final cell constants were calculated from the xyz centroids of 4048 strong reflections from the actual data collection after integration. 3 See Table S7 for additional crystal and refinement information. Structure solution and refinement The structure was solved using SIR and refined using SHELXL-2014/7. 5 The space group P2 1 /n was determined based on systematic absences. A direct-methods solution was calculated which provided most nonhydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. The final full matrix least squares refinement converged to R1 = (F 2, I > 2 (I)) and wr2 = (F 2, all data). Structure description The structure is the one suggested. The asymmetric unit contains one molecule in a general position. Unless noted otherwise all structural diagrams containing thermal displacement ellipsoids are drawn at the 50 % probability level. Data collection, structure solution, and structure refinement were conducted at the X-ray Crystallographic Facility, B51 Hutchison Hall, Department of Chemistry, University of Rochester. All publications arising from this report MUST either 1) include William W. Brennessel as a coauthor or 2) acknowledge William W. Brennessel and the X- ray Crystallographic Facility of the Department of Chemistry at the University of Rochester. S-55

56 1 APEX2, version ; Bruker AXS: Madison, WI, Sheldrick, G. M. SADABS, version 2014/3; University of Göttingen: Göttingen, Germany, SAINT, version 8.32B; Bruker AXS: Madison, WI, Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini, B.; Cascarano, G. L.; Giacovazzo, C.; Mallamo, M.; Mazzone, A.; Polidori, G.; Spagna, R. SIR2011: a new package for crystal structure determination and refinement, version 1.0; Istituto di Cristallografia: Bari, Italy, Sheldrick, G. M. SHELXL-2014/7; University of Göttingen: Göttingen, Germany, Some equations of interest: R int = F 2 o -< F 2 o > / F 2 o R1 = F o - F c / F o wr2 = [ [w(f o2 -F 2 c ) 2 ] / [w(f 2 o ) 2 ]] 1/2 where w = 1 / [ 2 (F o2 ) + (ap ) 2 + bp] and P = 1/3 max (0, F o2 ) + 2/3 F 2 c GOF = S = [ [w(f o2 -F 2 c ) 2 ] / (m-n )] 1/2 where m = number of reflections and n = number of parameters S-56

57 Table S-9. Crystal data and structure refinement for jonlm13. (2b) Identification code jonlm13 Empirical formula C20 H31 Mo N O5 P2 Formula weight Temperature 100.0(5) K Wavelength Å Crystal system monoclinic Space group P2 1 /n Unit cell dimensions a = (3) Å = 90 b = (3) Å = (4) c = (5) Å = 90 Volume (10) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1080 Crystal color, morphology yellow, plate Crystal size 0.18 x 0.14 x 0.05 mm 3 Theta range for data collection to Index ranges -16 h 16, -13 k 13, -25 l 25 Reflections collected Independent reflections 5567 [R(int) = ] Observed reflections 3838 Completeness to theta = % Absorption correction Multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5567 / 0 / 262 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S-57

58 Table S-10. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for jonlm13 (2b). U eq is defined as one third of the trace of the orthogonalized U ij tensor. x y z U eq Mo1 4160(1) 2351(1) 1305(1) 19(1) P1 5904(1) 3470(1) 1488(1) 20(1) P2 2174(1) 2262(1) 1121(1) 23(1) O1 4953(4) -488(3) 1399(3) 67(2) O2 3938(3) 2052(4) -361(2) 45(1) O3 4528(4) 1651(4) 2942(2) 53(1) O4 5486(3) 5021(3) 1343(2) 23(1) O5 1816(3) 3822(3) 1143(2) 29(1) N1 3651(3) 4410(3) 1240(2) 21(1) C1 4645(5) 563(5) 1348(3) 37(1) C2 3993(4) 2230(5) 234(3) 29(1) C3 4395(4) 2019(5) 2354(3) 31(1) C4 4399(4) 5339(4) 1259(2) 20(1) C5 4118(4) 6637(4) 1212(2) 24(1) C6 3026(4) 6957(5) 1148(3) 29(1) C7 2216(5) 6012(4) 1120(3) 28(1) C8 2584(4) 4750(4) 1164(3) 27(1) C9 6633(4) 3394(4) 805(3) 24(1) C (5) 2032(4) 708(3) 31(1) C (5) 4367(5) 900(3) 37(1) C (4) 3683(4) 2369(3) 24(1) C (4) 4223(5) 2936(3) 30(1) C (5) 2413(5) 2639(3) 38(1) C (4) 1792(5) 257(3) 27(1) C (5) 489(5) 9(3) 35(1) C (5) 2798(5) -329(3) 37(1) C (4) 1704(5) 1824(3) 31(1) C (5) 250(5) 1905(3) 40(1) C20 406(5) 2190(6) 1755(3) 44(2) S-58

59 Table S-11. Bond lengths [Å] and angles [ ] for jonlm13 (2b). Mo(1)-C(1) 1.961(5) C(11)-H(11C) Mo(1)-C(3) 1.997(5) C(12)-C(13) 1.525(6) Mo(1)-C(2) 2.029(5) C(12)-C(14) 1.536(6) Mo(1)-N(1) 2.241(4) C(12)-H(12A) Mo(1)-P(2) (14) C(13)-H(13A) Mo(1)-P(1) (13) C(13)-H(13B) P(1)-O(4) 1.703(3) C(13)-H(13C) P(1)-C(12) 1.836(5) C(14)-H(14A) P(1)-C(9) 1.837(5) C(14)-H(14B) P(2)-O(5) 1.698(3) C(14)-H(14C) P(2)-C(18) 1.837(5) C(15)-C(17) 1.532(7) P(2)-C(15) 1.845(5) C(15)-C(16) 1.537(7) O(1)-C(1) 1.160(6) C(15)-H(15A) O(2)-C(2) 1.152(6) C(16)-H(16A) O(3)-C(3) 1.167(6) C(16)-H(16B) O(4)-C(4) 1.355(5) C(16)-H(16C) O(5)-C(8) 1.357(6) C(17)-H(17A) N(1)-C(8) 1.340(6) C(17)-H(17B) N(1)-C(4) 1.341(6) C(17)-H(17C) C(4)-C(5) 1.400(6) C(18)-C(19) 1.532(7) C(5)-C(6) 1.369(7) C(18)-C(20) 1.532(7) C(5)-H(5A) C(18)-H(18A) C(6)-C(7) 1.403(7) C(19)-H(19A) C(6)-H(6A) C(19)-H(19D) C(7)-C(8) 1.393(6) C(19)-H(19B) C(7)-H(7A) C(20)-H(20D) C(9)-C(10) 1.536(6) C(20)-H(20A) C(9)-C(11) 1.537(7) C(20)-H(20B) C(9)-H(9A) C(1)-Mo(1)-C(3) 81.2(2) C(10)-H(10A) C(1)-Mo(1)-C(2) 85.0(2) C(10)-H(10B) C(3)-Mo(1)-C(2) 166.1(2) C(10)-H(10C) C(1)-Mo(1)-N(1) (18) C(11)-H(11A) C(3)-Mo(1)-N(1) 99.86(18) C(11)-H(11B) C(2)-Mo(1)-N(1) 93.94(17) S-59

60 C(1)-Mo(1)-P(2) (17) C(3)-Mo(1)-P(2) 87.23(15) C(2)-Mo(1)-P(2) 94.77(14) N(1)-Mo(1)-P(2) 76.54(10) C(1)-Mo(1)-P(1) (17) C(3)-Mo(1)-P(1) 96.03(14) C(2)-Mo(1)-P(1) 88.44(14) N(1)-Mo(1)-P(1) 76.42(10) P(2)-Mo(1)-P(1) (4) O(4)-P(1)-C(12) 97.87(19) O(4)-P(1)-C(9) 96.77(18) C(12)-P(1)-C(9) 106.5(2) O(4)-P(1)-Mo(1) (12) C(12)-P(1)-Mo(1) (16) C(9)-P(1)-Mo(1) (16) O(5)-P(2)-C(18) 96.7(2) O(5)-P(2)-C(15) 99.3(2) C(18)-P(2)-C(15) 104.5(2) O(5)-P(2)-Mo(1) (12) C(18)-P(2)-Mo(1) (18) C(15)-P(2)-Mo(1) (16) C(4)-O(4)-P(1) 119.7(3) C(8)-O(5)-P(2) 120.0(3) C(8)-N(1)-C(4) 118.0(4) C(8)-N(1)-Mo(1) 121.0(3) C(4)-N(1)-Mo(1) 120.9(3) O(1)-C(1)-Mo(1) 177.6(6) O(2)-C(2)-Mo(1) 173.8(5) O(3)-C(3)-Mo(1) 170.8(5) N(1)-C(4)-O(4) 119.2(4) N(1)-C(4)-C(5) 123.0(4) O(4)-C(4)-C(5) 117.8(4) C(6)-C(5)-C(4) 117.7(4) C(6)-C(5)-H(5A) C(4)-C(5)-H(5A) C(5)-C(6)-C(7) 121.0(4) C(5)-C(6)-H(6A) C(7)-C(6)-H(6A) C(8)-C(7)-C(6) 116.6(5) C(8)-C(7)-H(7A) C(6)-C(7)-H(7A) N(1)-C(8)-O(5) 118.7(4) N(1)-C(8)-C(7) 123.7(5) O(5)-C(8)-C(7) 117.5(5) C(10)-C(9)-C(11) 111.6(4) C(10)-C(9)-P(1) 112.1(3) C(11)-C(9)-P(1) 115.6(3) C(10)-C(9)-H(9A) C(11)-C(9)-H(9A) P(1)-C(9)-H(9A) C(9)-C(10)-H(10A) C(9)-C(10)-H(10B) H(10A)-C(10)-H(10B) C(9)-C(10)-H(10C) H(10A)-C(10)-H(10C) H(10B)-C(10)-H(10C) C(9)-C(11)-H(11A) C(9)-C(11)-H(11B) H(11A)-C(11)-H(11B) C(9)-C(11)-H(11C) H(11A)-C(11)-H(11C) H(11B)-C(11)-H(11C) C(13)-C(12)-C(14) 109.8(4) C(13)-C(12)-P(1) 111.6(3) C(14)-C(12)-P(1) 110.7(3) C(13)-C(12)-H(12A) C(14)-C(12)-H(12A) P(1)-C(12)-H(12A) C(12)-C(13)-H(13A) C(12)-C(13)-H(13B) H(13A)-C(13)-H(13B) C(12)-C(13)-H(13C) S-60

61 H(13A)-C(13)-H(13C) H(17A)-C(17)-H(17B) H(13B)-C(13)-H(13C) C(15)-C(17)-H(17C) C(12)-C(14)-H(14A) H(17A)-C(17)-H(17C) C(12)-C(14)-H(14B) H(17B)-C(17)-H(17C) H(14A)-C(14)-H(14B) C(19)-C(18)-C(20) 111.5(4) C(12)-C(14)-H(14C) C(19)-C(18)-P(2) 111.5(4) H(14A)-C(14)-H(14C) C(20)-C(18)-P(2) 115.5(4) H(14B)-C(14)-H(14C) C(19)-C(18)-H(18A) C(17)-C(15)-C(16) 109.9(4) C(20)-C(18)-H(18A) C(17)-C(15)-P(2) 110.5(3) P(2)-C(18)-H(18A) C(16)-C(15)-P(2) 110.0(4) C(18)-C(19)-H(19A) C(17)-C(15)-H(15A) C(18)-C(19)-H(19D) C(16)-C(15)-H(15A) H(19A)-C(19)-H(19D) P(2)-C(15)-H(15A) C(18)-C(19)-H(19B) C(15)-C(16)-H(16A) H(19A)-C(19)-H(19B) C(15)-C(16)-H(16B) H(19D)-C(19)-H(19B) H(16A)-C(16)-H(16B) C(18)-C(20)-H(20D) C(15)-C(16)-H(16C) C(18)-C(20)-H(20A) H(16A)-C(16)-H(16C) H(20D)-C(20)-H(20A) H(16B)-C(16)-H(16C) C(18)-C(20)-H(20B) C(15)-C(17)-H(17A) H(20D)-C(20)-H(20B) C(15)-C(17)-H(17B) H(20A)-C(20)-H(20B) Symmetry transformations used to generate equivalent atoms: S-61

62 Table S-12. Anisotropic displacement parameters (Å 2 x 10 3 ) for jonlm13 (2b). The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Mo1 26(1) 10(1) 23(1) -1(1) 10(1) -2(1) P1 25(1) 10(1) 26(1) 1(1) 11(1) 0(1) P2 26(1) 20(1) 24(1) -1(1) 10(1) -4(1) O1 76(4) 11(2) 122(4) 0(2) 42(3) 3(2) O2 44(2) 66(3) 27(2) -11(2) 14(2) -8(2) O3 52(3) 72(3) 33(2) 10(2) 10(2) -27(2) O4 23(2) 9(1) 38(2) 2(1) 11(2) 0(1) O5 26(2) 21(2) 41(2) -5(2) 14(2) -1(2) N1 27(2) 12(2) 25(2) 1(2) 12(2) 2(2) C1 42(3) 19(3) 52(4) -3(2) 18(3) -9(2) C2 25(3) 27(2) 35(3) -2(2) 8(2) -1(2) C3 25(3) 34(3) 33(3) 0(2) 6(2) -12(2) C4 32(3) 10(2) 21(2) -1(2) 12(2) 3(2) C5 34(3) 10(2) 28(3) 1(2) 12(2) 2(2) C6 39(3) 20(2) 29(3) 1(2) 11(2) 10(2) C7 34(3) 21(2) 30(3) -1(2) 13(2) 6(2) C8 36(3) 25(2) 21(3) -4(2) 12(2) -3(2) C9 29(3) 22(2) 25(3) 3(2) 12(2) 1(2) C10 42(3) 22(2) 37(3) 4(2) 22(3) 9(2) C11 41(3) 27(3) 52(4) 4(2) 29(3) -1(2) C12 25(3) 17(2) 29(3) -3(2) 6(2) -3(2) C13 34(3) 26(3) 30(3) -6(2) 8(2) -7(2) C14 44(3) 26(3) 37(3) 1(2) 3(3) 10(3) C15 26(3) 26(2) 28(3) 2(2) 9(2) -3(2) C16 36(3) 35(3) 33(3) -9(2) 9(3) -9(2) C17 41(3) 40(3) 30(3) 6(2) 10(3) -3(3) C18 28(3) 42(3) 24(3) -2(2) 10(2) -12(2) C19 46(4) 42(3) 31(3) 7(2) 10(3) -18(3) C20 34(3) 65(4) 38(3) 4(3) 17(3) -6(3) S-62

63 Table S-13. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for jonlm13 (2b). x y z U(eq) H5A H6A H7A H9A H10A H10B H10C H11A H11B H11C H12A H13A H13B H13C H14A H14B H14C H15A H16A H16B H16C H17A H17B H17C H18A H19A H19D H19B H20D H20A H20B S-63

64 Table S-14. Torsion angles [ ] for jonlm13 (2b). C12-P1-O4-C (3) O4-P1-C9-C (4) C9-P1-O4-C (3) C12-P1-C9-C (4) Mo1-P1-O4-C4 8.1(3) Mo1-P1-C9-C (4) C18-P2-O5-C (4) O4-P1-C9-C (4) C15-P2-O5-C (4) C12-P1-C9-C (4) Mo1-P2-O5-C8 7.7(4) Mo1-P1-C9-C (3) C8-N1-C4-O (4) O4-P1-C12-C (3) Mo1-N1-C4-O4-2.2(6) C9-P1-C12-C (3) C8-N1-C4-C5 0.8(7) Mo1-P1-C12-C (4) Mo1-N1-C4-C (3) O4-P1-C12-C (3) P1-O4-C4-N1-4.7(6) C9-P1-C12-C (4) P1-O4-C4-C (3) Mo1-P1-C12-C (4) N1-C4-C5-C6 0.3(7) O5-P2-C15-C (4) O4-C4-C5-C (4) C18-P2-C15-C (4) C4-C5-C6-C7-0.9(7) Mo1-P2-C15-C (4) C5-C6-C7-C8 0.3(7) O5-P2-C15-C (3) C4-N1-C8-O (4) C18-P2-C15-C (4) Mo1-N1-C8-O5 1.6(6) Mo1-P2-C15-C (4) C4-N1-C8-C7-1.5(7) O5-P2-C18-C (4) Mo1-N1-C8-C (4) C15-P2-C18-C (4) P2-O5-C8-N1-6.7(6) Mo1-P2-C18-C (4) P2-O5-C8-C (3) O5-P2-C18-C (4) C6-C7-C8-N1 1.0(7) C15-P2-C18-C (5) C6-C7-C8-O (4) Mo1-P2-C18-C (3) S-64

65 REFERENCE NUMBER: jonsc14 (2c) CRYSTAL STRUCTURE REPORT C 24 H 39 N O 5 P 2 W or (tbuponop)w(co) 3 Report prepared for: Dr. S. Chakraborty, Prof. W. Jones February 18, 2014 William W. Brennessel X-ray Crystallographic Facility Department of Chemistry, University of Rochester 120 Trustee Road Rochester, NY S-65

66 Data collection A crystal (0.20 x 0.20 x 0.16 mm 3 ) was placed onto the tip of a 0.1 mm diameter glass capillary tube or fiber and mounted on a Bruker SMART APEX II CCD platform diffractometer for a data collection at 100.0(5) K. 1 A preliminary set of cell constants and an orientation matrix were calculated from reflections harvested from three orthogonal wedges of reciprocal space. The full data collection was carried out using MoK radiation (graphite monochromator) with a frame time of 15 seconds and a detector distance of 3.99 cm. A randomly oriented region of reciprocal space was surveyed: six major sections of frames were collected with 0.50º steps in at six different settings and a detector position of -38º in 2. The intensity data were corrected for absorption. 2 Final cell constants were calculated from the xyz centroids of 3889 strong reflections from the actual data collection after integration. 3 See Table S13 for additional crystal and refinement information. Structure solution and refinement The structure was solved using SIR and refined using SHELXL The space group P2 1 /n was determined based on systematic absences. A direct-methods solution was calculated which provided most nonhydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. A lone peak of 5.18 electrons per Å 3, located 1.32 Å from atom H8D, has no chemical meaning and is likely due to low angle systematic contamination from a small misaligned region of the crystal (due to cracking upon placement into the coldstream). Because the quality of the overall structure was sufficient for the chemist's needs, a second crystal was not examined. Pseudomerohedral twinning was also considered because the cell can metrically transform to centered orthorhombic by a 180 degree rotation about direct lattice [100]. When refined as such, the minor component of twinning approached zero, and no improvements to the overall model were observed. The final full matrix least squares refinement converged to R1 = (F 2, I > 2 (I)) and wr2 = (F 2, all data). Structure description The structure is the one suggested. One tert-butyl group is modeled as disordered over two positions (83:17). The structure is isotypic with the molybdenum analog (local code JONRCR01). Unless noted otherwise all structural diagrams containing thermal displacement ellipsoids are drawn at the 50 % probability level. S-66

67 Data collection, structure solution, and structure refinement were conducted at the X-ray Crystallographic Facility, B51 Hutchison Hall, Department of Chemistry, University of Rochester. All publications arising from this report MUST either 1) include William W. Brennessel as a coauthor or 2) acknowledge William W. Brennessel and the X- ray Crystallographic Facility of the Department of Chemistry at the University of Rochester. 1 APEX2, version ; Bruker AXS: Madison, WI, Sheldrick, G. M. SADABS, version 2012/1; University of Göttingen: Göttingen, Germany, SAINT, version 8.34A; Bruker AXS: Madison, WI, Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini, B.; Cascarano, G. L.; Giacovazzo, C.; Mallamo, M.; Mazzone, A.; Polidori, G.; Spagna, R. SIR2011: a new package for crystal structure determination and refinement, version 1.0; Istituto di Cristallografia: Bari, Italy, Sheldrick, G. M. SHELXL-2014/1; University of Göttingen: Göttingen, Germany, Some equations of interest: R int = F 2 o -< F 2 o > / F 2 o R1 = F o - F c / F o wr2 = [ [w(f o2 -F 2 c ) 2 ] / [w(f 2 o ) 2 ]] 1/2 where w = 1 / [ 2 (F o2 ) + (ap ) 2 + bp] and P = 1/3 max (0, F o2 ) + 2/3 F 2 c GOF = S = [ [w(f o2 -F 2 c ) 2 ] / (m-n )] 1/2 where m = number of reflections and n = number of parameters S-67

68 Table S-15. Crystal data and structure refinement for jonsc14. Identification code jonsc14 Empirical formula C24 H39 N O5 P2 W Formula weight Temperature 100.0(5) K Wavelength Å Crystal system monoclinic Space group P2 1 /n Unit cell dimensions a = (16) Å = 90 b = (14) Å = (19) c = (16) Å = 90 Volume (5) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1336 Crystal color, morphology yellow-orange, wedge Crystal size 0.20 x 0.20 x 0.16 mm 3 Theta range for data collection to Index ranges -25 h 25, -22 k 23, -27 l 26 Reflections collected Independent reflections [R(int) = ] Observed reflections Completeness to theta = % Absorption correction Multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 7 / 344 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S-68

69 Table S-16. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for jonsc14 (2c). U eq is defined as one third of the trace of the orthogonalized U ij tensor. x y z U eq W1 9126(1) 8886(1) 1888(1) 9(1) P1 9612(1) 7085(1) 2190(1) 12(1) P2 9600(1) 10676(1) 1979(1) 10(1) O (1) 7090(1) 2240(1) 15(1) O (1) 10615(1) 2005(1) 13(1) O3 8273(1) 8748(1) -397(1) 24(1) O4 6811(1) 8997(1) 1335(1) 25(1) O5 8966(2) 9046(1) 3834(1) 30(1) N (1) 8857(1) 2193(1) 10(1) C (1) 7972(1) 2334(1) 12(1) C (1) 7924(1) 2560(1) 15(1) C (1) 8829(1) 2600(1) 16(1) C (1) 9747(1) 2409(1) 14(1) C (1) 9725(1) 2206(1) 11(1) C6a 8984(2) 11635(2) 966(2) 15(1) C7a 8140(2) 12202(2) 1087(2) 28(1) C8a 8479(3) 11060(2) -1(2) 32(1) C9a 9731(2) 12390(2) 893(2) 21(1) C6'e 8941(7) 11469(6) 839(5) 15(1) C7'e 9339(8) 11111(8) 135(7) 18(2) C8'e 9118(8) 12626(7) 968(8) 22(2) C9'e 7790(7) 11259(8) 404(8) 20(2) C (1) 11372(1) 3170(1) 17(1) C (2) 10716(2) 3951(1) 23(1) C (2) 11473(2) 3404(2) 29(1) C (2) 12430(1) 3230(2) 24(1) C (1) 6031(1) 1275(1) 16(1) C (2) 6473(2) 255(2) 28(1) C (2) 5544(2) 1408(2) 31(1) C (2) 5203(2) 1338(2) 28(1) C (1) 6557(1) 3451(1) 17(1) S-69

70 C (2) 7287(1) 4154(1) 22(1) C (2) 6541(2) 3674(2) 26(1) C (2) 5491(2) 3648(2) 26(1) C (1) 8793(1) 445(1) 14(1) C (1) 8944(1) 1519(1) 15(1) C (1) 8985(1) 3177(1) 17(1) S-70

71 Table S-17. Bond lengths [Å] and angles [ ] for jonsc14 (2c). W(1)-C(23) (17) C8a-H8Ba W(1)-C(24) (18) C8a-H8Ca W(1)-C(22) (17) C9a-H9Aa W(1)-N(1) (13) C9a-H9Ba W(1)-P(2) (5) C9a-H9Ca W(1)-P(1) (5) C6'e-C8'e 1.540(8) P(1)-O(1) (12) C6'e-C9'e 1.541(8) P(1)-C(14) (17) C6'e-C7'e 1.542(8) P(1)-C(18) (17) C7'e-H7De P(2)-O(2) (12) C7'e-H7Ee P(2)-C6a (18) C7'e-H7Fe P(2)-C6'e 1.889(5) C8'e-H8De P(2)-C(10) (17) C8'e-H8Ee O(1)-C(1) (19) C8'e-H8Fe O(2)-C(5) (18) C9'e-H9De O(3)-C(22) 1.161(2) C9'e-H9Ee O(4)-C(23) 1.167(2) C9'e-H9Fe O(5)-C(24) 1.160(2) C(10)-C(12) 1.534(3) N(1)-C(1) (19) C(10)-C(13) 1.540(3) N(1)-C(5) (19) C(10)-C(11) 1.548(3) C(1)-C(2) 1.387(2) C(11)-H(11A) C(2)-C(3) 1.387(2) C(11)-H(11B) C(2)-H(2) C(11)-H(11C) C(3)-C(4) 1.387(2) C(12)-H(12A) C(3)-H(3) C(12)-H(12B) C(4)-C(5) 1.389(2) C(12)-H(12C) C(4)-H(4) C(13)-H(13A) C6a-C8a 1.531(3) C(13)-H(13B) C6a-C9a 1.531(3) C(13)-H(13C) C6a-C7a 1.543(3) C(14)-C(15) 1.521(3) C7a-H7Aa C(14)-C(16) 1.539(3) C7a-H7Ba C(14)-C(17) 1.543(3) C7a-H7Ca C(15)-H(15A) C8a-H8Aa C(15)-H(15B) S-71

72 C(15)-H(15C) C(16)-H(16A) C(16)-H(16B) C(16)-H(16C) C(17)-H(17A) C(17)-H(17B) C(17)-H(17C) C(18)-C(20) 1.532(3) C(18)-C(21) 1.539(3) C(18)-C(19) 1.546(3) C(19)-H(19A) C(19)-H(19B) C(19)-H(19C) C(20)-H(20A) C(20)-H(20B) C(20)-H(20C) C(21)-H(21A) C(21)-H(21B) C(21)-H(21C) C(23)-W(1)-C(24) 77.10(7) C(23)-W(1)-C(22) 84.82(7) C(24)-W(1)-C(22) (7) C(23)-W(1)-N(1) (6) C(24)-W(1)-N(1) (6) C(22)-W(1)-N(1) 91.11(6) C(23)-W(1)-P(2) (5) C(24)-W(1)-P(2) 90.76(5) C(22)-W(1)-P(2) 93.79(4) N(1)-W(1)-P(2) 75.52(3) C(23)-W(1)-P(1) (5) C(24)-W(1)-P(1) 90.44(5) C(22)-W(1)-P(1) 94.24(4) N(1)-W(1)-P(1) 75.58(3) P(2)-W(1)-P(1) (14) O(1)-P(1)-C(14) 98.07(7) O(1)-P(1)-C(18) 97.02(7) C(14)-P(1)-C(18) (8) O(1)-P(1)-W(1) (4) C(14)-P(1)-W(1) (6) C(18)-P(1)-W(1) (6) O(2)-P(2)-C6a 98.19(9) O(2)-P(2)-C6'e 97.2(3) O(2)-P(2)-C(10) 96.82(7) C6a-P(2)-C(10) (9) C6'e-P(2)-C(10) 116.3(3) O(2)-P(2)-W(1) (4) C6a-P(2)-W(1) (7) C6'e-P(2)-W(1) 117.9(3) C(10)-P(2)-W(1) (6) C(1)-O(1)-P(1) (10) C(5)-O(2)-P(2) (10) C(1)-N(1)-C(5) (13) C(1)-N(1)-W(1) (10) C(5)-N(1)-W(1) (10) O(1)-C(1)-N(1) (13) O(1)-C(1)-C(2) (13) N(1)-C(1)-C(2) (14) C(1)-C(2)-C(3) (14) C(1)-C(2)-H(2) C(3)-C(2)-H(2) C(4)-C(3)-C(2) (15) C(4)-C(3)-H(3) C(2)-C(3)-H(3) C(3)-C(4)-C(5) (14) C(3)-C(4)-H(4) C(5)-C(4)-H(4) O(2)-C(5)-N(1) (13) O(2)-C(5)-C(4) (13) N(1)-C(5)-C(4) (13) C8a-C6a-C9a 106.7(2) C8a-C6a-C7a 107.7(2) C9a-C6a-C7a (18) S-72

73 C8a-C6a-P(2) (14) C9a-C6a-P(2) (15) C7a-C6a-P(2) (16) C6a-C7a-H7Aa C6a-C7a-H7Ba H7Aa-C7a-H7Ba C6a-C7a-H7Ca H7Aa-C7a-H7Ca H7Ba-C7a-H7Ca C6a-C8a-H8Aa C6a-C8a-H8Ba H8Aa-C8a-H8Ba C6a-C8a-H8Ca H8Aa-C8a-H8Ca H8Ba-C8a-H8Ca C6a-C9a-H9Aa C6a-C9a-H9Ba H9Aa-C9a-H9Ba C6a-C9a-H9Ca H9Aa-C9a-H9Ca H9Ba-C9a-H9Ca C8'e-C6'e-C9'e 108.8(6) C8'e-C6'e-C7'e 107.1(6) C9'e-C6'e-C7'e 110.4(7) C8'e-C6'e-P(2) 116.1(6) C9'e-C6'e-P(2) 107.2(6) C7'e-C6'e-P(2) 107.2(5) C6'e-C7'e-H7De C6'e-C7'e-H7Ee H7De-C7'e-H7Ee C6'e-C7'e-H7Fe H7De-C7'e-H7Fe H7Ee-C7'e-H7Fe C6'e-C8'e-H8De C6'e-C8'e-H8Ee H8De-C8'e-H8Ee C6'e-C8'e-H8Fe H8De-C8'e-H8Fe H8Ee-C8'e-H8Fe C6'e-C9'e-H9De C6'e-C9'e-H9Ee H9De-C9'e-H9Ee C6'e-C9'e-H9Fe H9De-C9'e-H9Fe H9Ee-C9'e-H9Fe C(12)-C(10)-C(13) (16) C(12)-C(10)-C(11) (17) C(13)-C(10)-C(11) (15) C(12)-C(10)-P(2) (13) C(13)-C(10)-P(2) (13) C(11)-C(10)-P(2) (12) C(10)-C(11)-H(11A) C(10)-C(11)-H(11B) H(11A)-C(11)-H(11B) C(10)-C(11)-H(11C) H(11A)-C(11)-H(11C) H(11B)-C(11)-H(11C) C(10)-C(12)-H(12A) C(10)-C(12)-H(12B) H(12A)-C(12)-H(12B) C(10)-C(12)-H(12C) H(12A)-C(12)-H(12C) H(12B)-C(12)-H(12C) C(10)-C(13)-H(13A) C(10)-C(13)-H(13B) H(13A)-C(13)-H(13B) C(10)-C(13)-H(13C) H(13A)-C(13)-H(13C) H(13B)-C(13)-H(13C) C(15)-C(14)-C(16) (17) C(15)-C(14)-C(17) (17) C(16)-C(14)-C(17) (16) S-73

74 C(15)-C(14)-P(1) (12) C(20)-C(18)-P(1) (13) C(16)-C(14)-P(1) (14) C(21)-C(18)-P(1) (13) C(17)-C(14)-P(1) (13) C(19)-C(18)-P(1) (12) C(14)-C(15)-H(15A) C(18)-C(19)-H(19A) C(14)-C(15)-H(15B) C(18)-C(19)-H(19B) H(15A)-C(15)-H(15B) H(19A)-C(19)-H(19B) C(14)-C(15)-H(15C) C(18)-C(19)-H(19C) H(15A)-C(15)-H(15C) H(19A)-C(19)-H(19C) H(15B)-C(15)-H(15C) H(19B)-C(19)-H(19C) C(14)-C(16)-H(16A) C(18)-C(20)-H(20A) C(14)-C(16)-H(16B) C(18)-C(20)-H(20B) H(16A)-C(16)-H(16B) H(20A)-C(20)-H(20B) C(14)-C(16)-H(16C) C(18)-C(20)-H(20C) H(16A)-C(16)-H(16C) H(20A)-C(20)-H(20C) H(16B)-C(16)-H(16C) H(20B)-C(20)-H(20C) C(14)-C(17)-H(17A) C(18)-C(21)-H(21A) C(14)-C(17)-H(17B) C(18)-C(21)-H(21B) H(17A)-C(17)-H(17B) H(21A)-C(21)-H(21B) C(14)-C(17)-H(17C) C(18)-C(21)-H(21C) H(17A)-C(17)-H(17C) H(21A)-C(21)-H(21C) H(17B)-C(17)-H(17C) H(21B)-C(21)-H(21C) C(20)-C(18)-C(21) (16) O(3)-C(22)-W(1) (16) C(20)-C(18)-C(19) (16) O(4)-C(23)-W(1) (15) C(21)-C(18)-C(19) (15) O(5)-C(24)-W(1) (17) S-74