Supporting Information

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1 Supporting Information Synthesis of pincer hydrido ruthenium olefin complexes for catalytic alkane dehydrogenation Yuxuan Zhang, Huaquan Fang, Wubing Yao, Xuebing Leng and Zheng Huang* State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai , China Crystal structures and crystallographic data for ruthenium(ii) complexes 2a, 3a, 4a and 4c... S2 Procedures for alkane dehydrogenation... S10 S1

2 Crystal structures and crystallographic data for ruthenium(ii) complexes 2a, 3a, 4a and 4c Figure S1. Crystal structure for ( ipr POCOP)RuCl(PPh 3 ) (2a). Table S1. Selected bond length for ( ipr POCOP)RuCl(PPh 3 ) (2a). Selected Bond Length Distance(Å) Ru(1)-C(1) (15) Ru(1)-P(3) (4) Ru(1)-P(1) (4) Ru(1)-P(2) (4) Ru(1)-Cl(1) (4) P(1)-O(1) (11) P(2)-O(2) (12) Table S2. Selected bond angles for ( ipr POCOP)RuCl(PPh 3 ) (2a). Selected Bond Angles (deg) C(1)-Ru(1)-P(3) 88.44(4) C(1)-Ru(1)-P(1) 77.03(4) P(3)-Ru(1)-P(1) (14) C(1)-Ru(1)-P(2) 79.23(4) P(3)-Ru(1)-P(2) (14) P(1)-Ru(1)-P(2) (15) C(1)-Ru(1)-Cl(1) (4) P(3)-Ru(1)-Cl(1) (15) P(1)-Ru(1)-Cl(1) (14) P(2)-Ru(1)-Cl(1) (14) O(1)-P(1)-Ru(1) (4) O(2)-P(2)-Ru(1) (4) S2

3 Figure S2. Crystal structure for ( ipr POCOP)RuCl(NBD) (3a) Table S3. Selected bond length for ( ipr POCOP)RuCl(NBD) (3a). Selected Bond Length Distance(Å) Ru(1)-C(1) 2.091(3) Ru(1)-C(19) 2.158(3) Ru(1)-C(20) 2.165(3) Ru(1)-C(23) 2.252(3) Ru(1)-C(22) 2.254(3) Ru(1)-P(2) (8) Ru(1)-P(1) (7) Ru(1)-Cl(1) (7) P(1)-O(1) 1.644(2) P(2)-O(2) 1.642(2) Table S4. Selected bond angles for ( ipr POCOP)RuCl(NBD) (3a). Selected Bond Angles (deg) C(19)-Ru(1)-C(20) 38.08(11) C(23)-Ru(1)-C(22) 35.92(11) C(1)-Ru(1)-P(2) 73.66(8) C(1)-Ru(1)-P(1) 76.84(8) P(2)-Ru(1)-P(1) (3) C(1)-Ru(1)-Cl(1) (7) S3

4 Figure S3. Crystal structure for ( ipr POCOP)RuH(NBD) (4a). Table S5. Selected bond length for ( ipr POCOP)RuH(NBD) (4a). Selected Bond Length Distance(Å) Ru(1)-C(1) (17) Ru(1)-C(24) 2.243(2) Ru(1)-C(25) (19) Ru(1)-C(19) (19) Ru(1)-C(20) 2.260(2) Ru(1)-P(1) (7) Ru(1)-P(2) (8) Ru(1)-H(1) 1.54(2) O(1)-P(1) (15) O(2)-P(2) (14) Table S6. Selected bond angles for ( ipr POCOP)RuH(NBD) (4a). Selected Bond Angles (deg) C(24)-Ru(1)-C(25) 36.03(8) C(19)-Ru(1)-C(20) 35.55(7) C(1)-Ru(1)-P(1) 76.08(6) C(1)-Ru(1)-P(2) 76.97(6) P(1)-Ru(1)-P(2) (19) C(1)-Ru(1)-H(1) 99.9(8) S4

5 Figure S4. Crystal structure for ( ipr PCP)RuH(NBD) (4c). Table S7. Selected bond length for ( ipr PCP)RuH(NBD) (4c). Selected Bond Length Distance(Å) Ru(1)-C(1) 2.127(3) Ru(1)-C(2) 2.224(3) Ru(1)-C(3) 2.207(3) Ru(1)-C(4) 2.258(3) Ru(1)-C(5) 2.263(3) Ru(1)-P(1) (8) Ru(1)-P(2) (8) P(1)-C(9) 1.832(3) P(2)-C(15) 1.840(3) Table S8. Selected bond angles for ( ipr PCP)RuH(NBD) (4c). Selected Bond Angles (deg) P(1)-Ru(1)-P(2) (3) C(1)-Ru(1)-P(1) 77.59(8) C(1)-Ru(1)-P(2) 78.75(9) C(3)-Ru(1)-C(2) 36.89(11) C(4)-Ru(1)-C(5) 35.73(12) S5

6 Table S9. Crystal data and structure refinement for ( ipr POCOP)RuCl(PPh 3 ) (2a). Empirical formula C36 H46 Cl O2 P3 Ru Formula weight Temperature Wavelength Crystal system 133(2) K Å Triclinic Space group P -1 Unit cell dimensions a = (6) Å a= (10). b = (6) Å b= (10). c = (10) Å g = (10). Volume (17) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 768 Crystal size x x mm 3 Theta range for data collection to Index ranges -14<=h<=14, -14<=k<=14, -18<=l<=25 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 396 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 S6

7 Table S10. Crystal data and structure refinement for ( ipr POCOP)RuCl(NBD) (3a). Empirical formula C25 H39 Cl O2 P2 Ru Formula weight Temperature Wavelength Crystal system 173(2) K Å Monoclinic Space group P 21/c Unit cell dimensions a = (6) Å a= 90. b = (3) Å b= (5). c = (6) Å g = 90. Volume (3) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1184 Crystal size x x mm 3 Theta range for data collection to Index ranges -11<=h<=11, -52<=k<=52, -13<=l<=14 Reflections collected Independent reflections 7946 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7946 / 0 / 287 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 S7

8 Table S11. Crystal data and structure refinement for ( ipr POCOP)RuH(NBD) (4a). Empirical formula C25 H40 O2 P2 Ru Formula weight Temperature Wavelength Crystal system 296(2) K Å Triclinic Space group P -1 Unit cell dimensions a = (3) Å a= (6). b = (3) Å b= (5). c = (4) Å g = (5). Volume (7) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 560 Crystal size x x mm 3 Theta range for data collection to Index ranges -14<=h<=14, -13<=k<=15, -18<=l<=18 Reflections collected Independent reflections 7646 [R(int) = ] Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7646 / 0 / 284 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient (4) Largest diff. peak and hole and e.å -3 S8

9 Table S12. Crystal data and structure refinement for ( ipr PCP)RuH(NBD) (4c). Empirical formula C27 H43 P2 Ru Formula weight Temperature Wavelength Crystal system 130 K Å Orthorhombic Space group I b a 2 Unit cell dimensions a = (10) Å a= 90. b = (19) Å b= 90. c = (7) Å g = 90. Volume (6) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2232 Crystal size 0.25 x 0.2 x 0.15 mm 3 Theta range for data collection to Index ranges -21<=h<=20, -42<=k<=42, -16<=l<=12 Reflections collected Independent reflections 6741 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6741 / 1 / 279 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.006(16) Extinction coefficient n/a Largest diff. peak and hole and e.å -3 S9

10 2. Procedures for alkane dehydrogenation General procedure for transfer dehydrogenation of cyclooctane with TBE. In an argon-filled glove-box, an oven-dried 5 ml thick-wall glass tube was charged with a ruthenium complex (4a-4d) (1.0 mmol/l, 2.0 mg for 4a, 4c and 4d, 3.0 mg for 2b, 3b and 4b), cyclooctane, and tert-butylethene (0.35 mol/l) as a hydrogen acceptor. The tube was sealed with a teflon plug under an argon atmosphere, and the solution stirred in a 200 C oil bath. Periodically, the flask was removed from the bath and cooled to room temperature. An aliquot was removed from the flask and analyzed by GC. Turnover numbers were calculated from the ratio of the amount of tert-butylethane (TBA) produced against the catalyst amount added. General procedure for transfer dehydrogenation of n-octane with TBE. In an argon-filled glove-box, an oven-dried 5 ml thick-wall glass tube was charged with a ruthenium complex (4a-4c, 6) (2.0 mmol/l, 3 mg for 4a and 4c, 4 mg for 4b) n-octane and mesitylene (0.2 mol/l), tert-butylethene (0.4 mol/l) was then added as a hydrogen acceptor. The tube was sealed with a teflon plug under an argon atmosphere, and the solution stirred in a 200 C oil bath. Periodically, the flask was removed from the bath and cooled to room temperature. An aliquot was removed from the flask and analyzed by GC. Acceptorless dehydrogenation of cyclooctane. In an argon-filled glove-box, an oven-dried 5 ml thick-wall glass tube was charged with a ruthenium complex 4a or 4b (4.0 µmol) and 1.63 ml of COA (3000 equiv, 12 mmol). After attaching a condenser to the tube, the mixture was stirred at 200 o C under a constant argon flow. A three-way piece was placed on top of the condenser to remove the liberated H 2 gas. After the reaction, the tube was cooled to room temperature and an aliquot was removed for GC analysis. Turnover numbers were calculated from the ratio of the amount of COE produced against the catalyst amount added. Alternatively, the reactions can be carried out in a sealed tube. In an argon-filled glove-box, an oven-dried 10 or 50 ml thick-wall glass tube was charged with a ruthenium complex 4b (2.0 mg, 2.72 µmmol, 1.0 mmol/l) and cyclooctane (2.7 ml, 20.0 mmol). The tube was sealed with a teflon plug under an argon atmosphere, and the solution stirred in a 200 C oil bath. After the reaction, the flask was removed from the bath and cooled to room temperature. An aliquot was removed from the flask and analyzed by GC. Turnover numbers were calculated from the ratio of the amount of COE produced against the catalyst amount added. S10