department of chemistry and biochemistry, university of ... · reactions of a quintuply bonded...

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Jingmei Shen,a Glenn P. A. Yap,a Jan-Philipp Wernerb and Klaus H. Theopold*a

a Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716

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Contents:

• Synthesis and characterization of Cr Complexes • Single crystal X-ray diffraction studies • Computational details

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Fig. 1S The molecular structure of 2b with thermal ellipsoids at the 30% probability level; H-‐

atoms and ligand isopropyl groups have been omitted for clarity. Selected distances [Å] and

angles [º]: Cr1–Cr2 1.9361(7), Cr1–N1 1.908(2), Cr1–N4 1.893(2), Cr2–N2 1.926(2), Cr2–N3

1.945(2), Cr1–C56 2.073(3), Cr2–C55 1.963(3), C55–C56 1.315(4), N1–C1 1.376(3), C1–C2

1.355(4), N2–C2 1.368(3), N3–C27 1.372(3), C27–C28 1.347(4), N4–C28 1.380(3), N1–Cr1–Cr2 106.16(6), N1–Cr1–N4 142.37(9), Cr2–Cr1–N4 102.66(6), N1–Cr1–C56 106.69(11), Cr2–Cr1–C56 66.97(9), N4–Cr1–C56 106.57(11), N2–Cr2–N3 126.13(9), N2–Cr2–Cr1 103.96(6), N3–Cr2–Cr1

103.39(6), N2–Cr2–C55 118.42(11), N3–Cr2–C55 108.12(11), Cr1–Cr2–C55 87.78(9).


6

Fig. 2S The molecular structure of 2c.toluene with thermal ellipsoids at the 30% probability level;

H-‐atoms, solvent molecules and ligand isopropyl groups and toluene solvent molecule have

been omitted for clarity. Selected distances [Å] and angles [º]: Cr1–Cr2 1.9186(7), Cr1–N1

1.935(2), Cr1–N3 1.928(2), Cr2–N2 1.915(2), Cr2–N4 1.910(2), Cr1–C53 1.992(3), Cr2–C54

2.056(3), C53–C54 1.339(4), N1–C1 1.366(3), C1–C2 1.355(4), N2–C2 1.378(3), N3–C27 1.370(3), C27–C28 1.345(4), N4–C28 1.380(3), N1–Cr1–Cr2 104.06(7), N1–Cr1–N3 129.12(9), Cr2–Cr1–N3 105.56(7), N1–Cr1–C53 119.99(11), Cr2–Cr1–C53 81.04(8), N3–Cr1–C53 104.85(11), N2–Cr2–N4

134.28(9), N2–Cr2–Cr1 106.32(6), N4–Cr2–Cr1 103.51(6), N2–Cr2–C54 110.11(11), N4–Cr2–C54 111.55(10), Cr1–Cr2–C54 72.29(8).


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Calculations. Geometry optimizations of the full structures were performed using gradient-‐corrected density-‐functional theory (DFT) in C1 symmetry. Exchange and correlation were treated

by a combination of Becke's exchange (B) and Lee, Yang and Parr's correlation (LYP) functional (BLYP).3-‐5 A self-‐consistent-‐field (SCF) convergence criterion of 10-‐6 hartree and the standard grid (m3) for numerical quadrature were used.6 Basis sets of double-‐zeta quality with polarization

functions on all atoms (def2-‐SVP)7 were used for all atoms except for the metal where we used basis sets of triple-‐zeta quality with polarization functions for the valence electrons (LANL08(f)) and treated the core electrons by an effective core potential (LANL2DZ ECP). For structure

optimizations all energy and gradient calculations were carried out using the TURBOMOLE V5.10

suite of programs 8 within the multipole accelerated RI-‐J approximation (MARI-‐J).9 The geometry

optimizations were driven by Gaussian 03 using the Berny algorithm employing redundant internal coordinates and standard convergence criteria.10 Initially the functionals BP86, PBE, BLYP, TPSS, B3LYP, PBE0, VSXC, tHCTH, B3PW91 were considered and their performances in

reproducing the crystallographic structure of 1 were compared. BLYP was selected for giving closest agreement with the experimental data. All reported structural parameters refer to singlet ground state structures.

For NBO/NPA analysis single point calculations with the same basis sets, ECPs and functional were performed with the ORCA 2.7.0 program to generate gennbo input files. These were processed with the gennbo program (version 5.0).

Single point energy calculations employing full electron basis sets of triple-‐z quality with polarization functions for all atoms (def2-‐TZVP) were done with the ORCA 2.7.0 program.11 The resolution of identity (RI) approximation as well as the chain of spheres approximation (RIJCOSX)

were used.

References 1. G. M. Sheldrick, Acta Crystallographica Section A, 2008, 64, 112-‐122. 2. A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7-‐13. 3. J. P. Perdew, Physical Review B, 1986, 33, 8822-‐8824. 4. J. P. Perdew, Physical Review B, 1986, 34, 7406-‐7406. 5. A. D. Becke, Physical Review A, 1988, 38, 3098-‐3100. 6. O. Treutler and R. Ahlrichs, J. Chem. Phys., 1995, 102, 346-‐354. 7. F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, 3297-‐3305. 8. TURBOMOLE V5.10 2008, a development of University of Karlsruhe and

Forschungszentrum Karlsruhe GmbH, 1989-‐2007, TURBOMOLE GmbH, since 2007; available from http://www.turbomole.com.

9. M. Sierka, A. Hogekamp and R. Ahlrichs, J. Chem. Phys., 2003, 118, 9136-‐9148. 10. Gaussian 03, Revision E.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;

Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.;


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Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-‐Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT, 2004.

11. Neese, F. ORCA -‐ an ab initio, Density Functional and Semiempirical program package, Version 2.6. University of Bonn, 2008.


department of chemistry and biochemistry, university of ... · reactions of a quintuply bonded...

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