Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide
Abstract
:1. Introduction
2. Results and Discussion
2.1. Preparation of Cationic Ruthenium Vinylidene Complexes 2a–e
C(36)–Ru(1) | 1.841(4) | C(36)–C(37) | 1.326(6) |
C(37)–C(44) | 1.538(6) | C(44)–C(45) | 1.515(6) |
P(1)–Ru(1) | 2.3380(10) | C(45)–C(46) | 1.321(6) |
P(2)–Ru(1) | 2.3104(10) | P(1)–Ru(1)–P(2) | 83.29(3) |
C(37)–C(36)–Ru(1) | 177.2(4) | C(36)–C(37)–C(44) | 119.1(4) |
2.2. Reactivity of the Vinylidene Complexes with TMSN3
N(1)–Ru(1) | 2.031(4) | C(27)–N(1) | 1.130(7) |
C(27)–C(28) | 1.494(9) | C(28)–C(35) | 1.515(10) |
P(1)–Ru(1) | 2.2637(13) | P(2)–Ru(1) | 2.2989(15) |
C(27)–N(1)–Ru(1) | 174.1(6) | N(1)–C(27)–C(28) | 176.8(8) |
P(1)-Ru(1)-P(2) | 84.34(5) | N(1)-Ru(1)-P(1) | 88.88(12) |
N(1)-Ru(1)-P(2) | 92.02(15) |
2a | 3a | |
---|---|---|
Empirical formula | C46H41IP2Ru | C46H42INP2Ru |
Temperature | 200(2) K | 200(2) K |
Crystal system | Orthorhombic | Monoclinic |
Space group | P n a 21 | P 21/n |
a, Å | 22.1483(8) | 10.4855(3) |
b, Å | 11.8391(5) | 19.1064(6) |
c, Å | 14.4101(6) | 19.8563(6) |
α, deg | 90 | 90 |
β, deg | 90 | 92.248(2) |
γ, deg | 90 | 90 |
Volume, Å3 | 3778.6(3) | 3975.0(2) |
Z | 4 | 4 |
Crystal size, mm3 | 0.27 × 0.14 × 0.11 | 0.28 × 0.24 × 0.08 |
Refinement method | Full-matrix least-squares on F2 | Full-matrix least-squares on F2 |
Flack parameters | −0.013(14) | |
Final R indices [I > 2sigma(I)] | R1 = 0.0240, wR2 = 0.0548 | R1= 0.0465, wR2 = 0.1133 |
R indices (all data) | R1 = 0.0283, wR2 = 0.0662 | R1 = 0.0682, wR2 = 0.1318 |
0.311 and −0.323 e | 1.323 and −0.897 e | |
Largest diff. peak and hole, Å−3 | 776702 | 776705 |
CCDC number |
2.3. Deprotonation Reaction of the Vinylidene Complexes
2.4. Reaction of Cyclopropenyl Complexes with TMSN3
2.5. Reaction of Furyl Complexes with TMSN3
3. Experimental
3.1. General
3.2. Synthesis of [(η5-C9H7)(dppe)Ru=C=C(Ph)CH2CH=CH2][I] (2a)
3.3. Synthesis of [(η5-C9H7)(dppe)Ru=C=C(Ph)CH2CO2CH3][Br] (2b)
3.4. Synthesis of [(η5-C9H7)(dppe)Ru=C=C(Ph)CH2CO2C2H5][I] (2c)
3.5. Synthesis of [(η5-C9H7)(dppe)Ru=C=C(Ph)CH2CH=CHCO2CH3][Br] (2d)
3.6. Synthesis of [(η5-C9H7)(dppe)Ru=C=C(Ph)CH2C≡CH][Br] (2e)
3.7. Synthesis of the N-Coordinated Complexes [(η5-C9H7)(dppe)Ru–NCCH(Ph)CH2CH=CH2][I] (3a)
3.8. Synthesis of the N-Coordinated Complexes [(η5-C9H7)(dppe)Ru–NCCH(Ph)CH2CO2CH3][Br] (3b)
3.9. Synthesis of the N-Coordinated Complexes [(η5-C9H7)(dppe)Ru–NCCH(Ph)CH2CO2C2H5][I] (3c)
3.10. Synthesis of the N-Coordinated Complexes [(η5-C9H7)(dppe)Ru–NCCH(Ph)CH2CH=CH CO2CH3] [Br] (3d)
3.11. Synthesis of the N-Coordinated Complexes [(η5-C9H7)(dppe)Ru–NCCH(Ph)CH2C≡CH][Br](3e)
3.12. Synthesis of Cyclopropenylruthenium Complex (η5-C9H7)(dppe)Ru–C=C(Ph)CH-CH=CH2 (4a )
3.13. Synthesis of Furylruthenium Complex (η5-C9H7)(dppe)Ru–C=C(Ph)CH=C(OCH3)O (4b)
3.14. Synthesis of Furylruthenium Complex (η5-C9H7)(dppe)Ru–C=C(Ph)CH=C(OC2H5)O (4c)
3.15. Synthesis of Cyclopropenylruthenium Complex (η5-C9H7)(dppe)Ru–C=C(Ph)CHCH=CHC(O) OCH3 (4d)
3.16. Reaction of 4a with TMSN3
3.17. Reaction of 4b with TMSN3
3.18. Reaction of 4c with TMSN3
3.19. Reaction of 4d with TMSN3
3.20. X-ray Analysis of 2a and 3a
4. Conclusions
Acknowledgments
References
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Sung, H.-L.; Her, T.-M.; Su, W.-H.; Cheng, C.-P. Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide. Molecules 2012, 17, 8533-8553. https://doi.org/10.3390/molecules17078533
Sung H-L, Her T-M, Su W-H, Cheng C-P. Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide. Molecules. 2012; 17(7):8533-8553. https://doi.org/10.3390/molecules17078533
Chicago/Turabian StyleSung, Hui-Ling, Tze-Min Her, Wen-Hsien Su, and Chin-Pao Cheng. 2012. "Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide" Molecules 17, no. 7: 8533-8553. https://doi.org/10.3390/molecules17078533