Stepwise Construction of the CrCr Quintuple Bond and Its Destruction upon Axial Coordination†
Yu-Lun Huang
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorDuan-Yen Lu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorHsien-Cheng Yu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorProf. Dr. Jen-Shiang K. Yu
Institute of Bioinformatics and Systems Biology and Department of Biological Science and Technology, National Chiao Tung University, Hsinchu, 30010 (Taiwan)
Search for more papers by this authorChia-Wei Hsu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorTing-Shen Kuo
Department of Chemistry, National Taiwan Normal University, Taipei 11677 (Taiwan)
Search for more papers by this authorDr. Gene-Hsiang Lee
Department of Chemistry, National Taiwan University, Taipei 10617 (Taiwan)
Search for more papers by this authorProf. Dr. Yu Wang
Department of Chemistry, National Taiwan University, Taipei 10617 (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Yi-Chou Tsai
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)Search for more papers by this authorYu-Lun Huang
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorDuan-Yen Lu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorHsien-Cheng Yu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorProf. Dr. Jen-Shiang K. Yu
Institute of Bioinformatics and Systems Biology and Department of Biological Science and Technology, National Chiao Tung University, Hsinchu, 30010 (Taiwan)
Search for more papers by this authorChia-Wei Hsu
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Search for more papers by this authorTing-Shen Kuo
Department of Chemistry, National Taiwan Normal University, Taipei 11677 (Taiwan)
Search for more papers by this authorDr. Gene-Hsiang Lee
Department of Chemistry, National Taiwan University, Taipei 10617 (Taiwan)
Search for more papers by this authorProf. Dr. Yu Wang
Department of Chemistry, National Taiwan University, Taipei 10617 (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Yi-Chou Tsai
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013 (Taiwan)Search for more papers by this authorWe are grateful to the National Science Council, Taiwan for financial support under grants NSC 99-2113M-007-012-MY3 (Y.C.T.) and 100-2627-B-009-001 (J.S.K.Y.), and the “Center for Bioinformatics Research of Aiming for the Top University Program” of NCTU and MoE, Taiwan.
Graphical Abstract
Give me five! Terdentate 2,6-diamidopyridyl ligands were used to stabilize the CrCr quintuple bond and have made it possible to isolate and characterize not only the CrCr quintuple-bonded complex, but also the mixed-valent intermediates (CrI and CrII), which are important species in the formation of type I quintuple-bonded complexes.
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, a=10.9399(15), b=13.3874(19), c=14.825(2) Å, α=70.668(2), β=70.474(2), γ=79.147(2)°, V=1923.6(5) Å3, Z=1, ρcalcd=1.051 Mg m−3, μ=0.325 mm−1, reflections collected: 11 009, independent reflections: 6687 (Rint=0.0267), final R indices [I>2σ(I)]: R1=0.0603, wR2=0.18084, R indices (all data): R1=0.0844, wR2=0.1981; 4: C54H106N6Cr2O2Si4, Mr=1097.81, T=200(2) K, monoclinic, space group P21/c, a=15.6863(3), b=19.2132(4), c=20.4594(5) Å, β=93.9640(10)°, V=6151.4(2) Å3, Z=4, ρcalcd=1.175 Mg m−3, μ=0.473 mm−1, reflections collected: 52063, independent reflections: 10790 (Rint=0.0532), final R indices [I>2σ(I)]: R1=0.0451, wR2=0.1116, R indices (all data): R1=0.0820, wR2=0.1393; 5⋅C4H10O: C80H122N6Cr2KO8: Mr=1438.94, T=200(2) K, monoclinic, space group P21/c, a=16.4037(2), b=15.7947(2), c=33.2294(5) Å, β=103.3030(10)°, V=8378.44(19) Å3, Z=4, ρcalcd=1.141 Mg m−3, μ=0.362 mm−1, reflections collected: 41494, independent reflections: 15 013 (Rint=0.0878), final R indices [I>2σ(I)]: R1=0.0720, wR2=0.1952, R indices (all data): R1=0.1300, wR2=0.2612; 6: C66H132N6Cr2KO8Si4: Mr=1393.24, T=200(2) K, tetragonal, space group 
, a=16.9265(3) Å, b=16.9265(3) Å, c=27.3011(5) Å, V=7821.9(2) Å3, Z=4, ρcalcd=1.183 Mg m−3, μ=0.443 mm−1, reflections collected: 22 457, independent reflections: 6876 (Rint=0.0360), final R indices [I>2σ(I)]: R1=0.0734, wR2=0.1985, R indices (all data): R1=0.0831, wR2=0.2088; 7⋅2 C4H10O: C76H118N6Cr2K2O4: Mr=1361.96, T=200(2) K, monoclinic, space group P21/n, a=9.91160(10), b=28.8440(3), c=13.7416(2) Å, β=90.4560(10)°, V=3928.46(8) Å3, Z=2, ρcalcd=1.151 Mg m−3, μ=0.430 mm−1, reflections collected: 36 327, independent reflections: 7199 (Rint=0.0765), final R indices [I>2σ(I)]: R1=0.0625, wR2=0.1598, R indices (all data): R1=0.0990, wR2=0.1983; 8⋅C7H8: C86H115N6CrK2O6: Mr=1459.04, T=200(2) K, triclinic, space group 
, a=14.5434(8), b=15.8602(9), c=22.8046(11) Å, α=78.569(3), β=72.312(3), γ=63.613(3)°, V=4477.0(4) Å3, Z=2, ρcalcd=1.082 Mg m−3, μ=0.270 mm−1, reflections collected: 37 371, independent reflections: 15 709 (Rint=0.0530), final R indices [I>2σ(I)]: R1=0.0978, wR2=0.2947, R indices (all data): R1=0.1806, wR2=0.3296; 10: C42H54N4Cr2O2: Mr=750.89, T=200(2) K, triclinic, space group 
, a=8.6139(3), b=10.8806(3), c=11.6811(4) Å, α=83.5650(10), β=81.9330(10), γ=68.575(2)°, V=1006.87(6) Å3, Z=1, ρcalcd=1.238 Mg m−3, μ=0.578 mm−1, reflections collected: 13 674, independent reflections: 3627 (Rint=0.0759), final R indices [I>2σ(I)]: R1=0.0679, wR2=0.1686, R indices (all data): R1=0.0959, wR2=0.1976; 11⋅2 MeTHF: C44H56N4Cr2O2: Mr=776.93, T=150(2) K, monoclinic, space group P21/n, a=10.7474(1), b=22.6841(2), c=17.4934(2) Å, β=104.7263(6)°, V=4124.71(7) Å3, Z=4, ρcalcd=1.251 Mg m−3, μ=0.567 mm−1, reflections collected: 26 280, independent reflections: 9447 (Rint=0.0310), final R indices [I>2σ(I)]: R1=0.0506, wR2=0.1484, R indices (all data): R1=0.0722, wR2=0.1654, CCDC 843643 (3⋅n-C6H14), 843644 (4), 843645 (5⋅C4H10O), 843646 (6), 843647 (7⋅2 C4H10O), 871483 (8⋅C7H8), 728851 (10), 728852 (11) 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.
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