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21
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53349151216
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P1, a, 12.3740(7, b, 12.9060(8, c, 15.1170(10) Å; α, 71.269(5, β, 75.700(5, γ, 68.868(5)° and R1, 0.0375 (I > 2σ(I, wR2, 0.0900 all data
-
2 = 0.0900 (all data).
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22
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0001499592
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2 complexes in which deprotonated aminopyridines act as bridging ligands: a F. A. Cotton, R. H. Niswander, J. C. Sekutowski, Inorg. Chem. 1978, 17, 3541-3545;
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2 complexes in which deprotonated aminopyridines act as bridging ligands: a) F. A. Cotton, R. H. Niswander, J. C. Sekutowski, Inorg. Chem. 1978, 17, 3541-3545;
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23
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37049075618
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0001832263
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c) F. A. Cotton, L. M. Daniels, C. A. Murillo, I. Pascual, Inorg. Chem. Commun. 1998, 1, 1-3;
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d) F. A. Cotton, L. M. Daniels, C. A. Murillo, I. Pascual, H.-C. Zhou, J. Am. Chem. Soc. 1999, 121, 6856-6861;
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0035805712
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e) F. A. Cotton, L. M. Daniels, P. Lei, C. A. Murillo, X. Wang, Inorg. Chem. 2001, 40, 2778-2784;
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Cotton, F.A.1
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33746244008
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f) R. Clerac, F. A. Cotton, S. P. Jeffery, C. A. Murillo, X. Wang, Dalton Trans. 2003, 3022-3027.
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Clerac, R.1
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33846492503
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S. Deeken, G. Motz, R. Kempe, Z. Anorg. Allg. Chem. 2007, 633, 320-325.
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Deeken, S.1
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29
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53349105241
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P1, a, 9.2100(12, b, 12.2290(14, c, 12.6890(15) Å α, 94.314(9, β, 105.714(10, γ, 108.185(10)° and R1, 0.0570 (I > 2σ(I, wR2, 0.1226 all data
-
2 = 0.1226 (all data).
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-
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32
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20644438873
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-
The calculations of the electronic structure were carried out at the DFT level with the program ADF: a G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Comput. Chem. 2001, 22, 931-967;
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The calculations of the electronic structure were carried out at the DFT level with the program ADF: a) G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Comput. Chem. 2001, 22, 931-967;
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33
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0032221816
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b) C. Fonseca Guerra, J. G. Snijders, G. te Velde, E. J. Baerends, Theor. Chem. Acc. 1998, 99, 391-403;
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Theor. Chem. Acc
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Fonseca Guerra, C.1
Snijders, J.G.2
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Baerends, E.J.4
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34
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4243553426
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ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com. The BLYP functional was used: d A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100;
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c) ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com. The BLYP functional was used: d) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100;
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35
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0345491105
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e) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789.
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Phys. Rev. B
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Lee, C.1
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36
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53349085939
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In the case of single-point energy calculations, all electrons were explicitly included using a TZ2P basis set (triple ζ, 2 sets of polarization functions) for each type of atom. The structure optimizations [19] were performed within the frozen-core approximation (C,N: 1s2 core; Cr: 1s22s2p6 core) using the corresponding TZP or TZ2P basis set. Calculation of the delocalization index was performed on the basis of a DFT (BLYP functional) single-point calculation with the Gaussian03 program system: f) M. J. Frisch et al, entire citation: see Supporting Information, Gaussian 03, Revision C.02, Gaussian, Inc, Wallingford, CT, 2004
-
6 core) using the corresponding TZP or TZ2P basis set. Calculation of the delocalization index was performed on the basis of a DFT (BLYP functional) single-point calculation with the Gaussian03 program system: f) M. J. Frisch et al. (entire citation: see Supporting Information), Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford, CT, 2004.
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37
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26344435738
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Herein, the corresponding TZVP basis set was used: g A. Schaefer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577;
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Herein, the corresponding TZVP basis set was used: g) A. Schaefer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577;
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38
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h) A. Schaefer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835.
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J. Chem. Phys
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Schaefer, A.1
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Ahlrichs, R.3
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39
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53349110751
-
-
The ELI-D is a scalar field which is defined in position space and momentum space. Roughly, ELI-D (γsD) in position space can be regarded as a quasi-continuous weighted electronic charge distribution ρσ (the σ-spin electron density, where the weighting factor ṼD (the so-called pair-function) is a local measure for the needed to build a same-spin (spin σ) electron pair: γsD(r, ρσ(r) x ṼD(r) The values for ELI-D are limited to the range of positive numbers. Typically, ELI-D values up to 2.5 (except for H atoms) can be found in the chemically relevant valence region for molecules. ELI-D has been defined at explicitly correlated and at uncorrelated quantum chemical level
-
D(r) The values for ELI-D are limited to the range of positive numbers. Typically, ELI-D values up to 2.5 (except for H atoms) can be found in the chemically relevant valence region for molecules. ELI-D has been defined at explicitly correlated and at uncorrelated quantum chemical level.
-
-
-
-
40
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36549100412
-
-
At the Hartree-Fock level, the ELI-D formula simplifies and strongly resembles the inverse kernel of the electron localization function (ELF) defined by Becke and Edgecombe: b) A. D. Becke, K. E. Edgecombe, J. Chem. Phys. 1990, 92, 5397-5403
-
At the Hartree-Fock level, the ELI-D formula simplifies and strongly resembles the inverse kernel of the electron localization function (ELF) defined by Becke and Edgecombe: b) A. D. Becke, K. E. Edgecombe, J. Chem. Phys. 1990, 92, 5397-5403.
-
-
-
-
41
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1342283608
-
-
Nevertheless, ELI-D should not be regarded as a generalization of the ELF. Although it is in a certain sense related to ELF, the ELI-D represents a separate quantity, which reflects one possible interpretation of the Becke ELF kernel at the correlated level of theory: c M. Kohout, Int. J. Quantum Chem. 2004, 97, 651-658;
-
Nevertheless, ELI-D should not be regarded as a generalization of the ELF. Although it is in a certain sense related to ELF, the ELI-D represents a separate quantity, which reflects one possible interpretation of the Becke ELF kernel at the correlated level of theory: c) M. Kohout, Int. J. Quantum Chem. 2004, 97, 651-658;
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42
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11944253042
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d) M. Kohout, K. Pernal, F. R. Wagner, Yu. Grin, Theor. Chem. Acc. 2004, 112, 453-459;
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Theor. Chem. Acc
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Kohout, M.1
Pernal, K.2
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43
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33646346609
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e) M. Kohout, F. R. Wagner, Yu. Grin, Int. J. Quantum Chem. 2006, 106, 1499-1507;
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Kohout, M.1
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34547230606
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g) F. R. Wagner, V. Bezugly, M. Kohout, Yu. Grin, Chem. Eur. J. 2007, 13, 5724-5741;
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43349089108
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h) M. Kohout, F. R. Wagner, Yu. Grin, Theor. Chem. Acc. 2008, 119, 413-420.
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Theor. Chem. Acc
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Kohout, M.1
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47
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0000046848
-
-
The delocalization index δ(A,B) is a quantitative measure for the sharing of electrons between two non-overlapping regions A and B in position space: a) X. Fradera, M. A. Austen, R. F. W. Bader, J. Phys. Chem. A 1999, 103, 304-314;
-
The delocalization index δ(A,B) is a quantitative measure for the sharing of electrons between two non-overlapping regions A and B in position space: a) X. Fradera, M. A. Austen, R. F. W. Bader, J. Phys. Chem. A 1999, 103, 304-314;
-
-
-
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49
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53349122384
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Model 4a was obtained by the exclusive relaxation of the Hatom positions based on the structural data of 4. On the basis of 4a in model 4b the Cr-Cr distance was relaxed, which led to a shortening of the bond to 1.69 Å. A radical simplification of the model by substituting all substituents on the deprotonated aminopyridine with H leads to model 4′ a, for which only the newly added H-atom positions were relaxed. Therefore, the Cr, N, and C atom positions of molecule 4′a shown in Figure 3 are identical with those for model 4a and of the experimental structure 4. Starting from 4′a, the complex was completely relaxed (model 4′b, which led to a planar molecule (C 2h symmetry) with a Cr-Cr distance of 1.68 Å.
-
2h symmetry) with a Cr-Cr distance of 1.68 Å. The consistent shortening of the Cr-Cr distance obtained by the present DFT(BLYP) calculations in complex 4b with the original ligand and in complex 4′b with the model ligand is caused by an incomplete treatment of the electron correlation in these calculations. It shows that the experimentally found short Cr-Cr distance is not caused by packing effects. For the coordinates of the models, see the Supporting Information.
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-
-
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50
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53349114469
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M. Kohout, program DGrid, version 4.3, Dresden 2008
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a) M. Kohout, program DGrid, version 4.3, Dresden 2008.
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51
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53349137648
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M. Kohout, program Basin, version 4.2, Dresden, 2007
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b) M. Kohout, program Basin, version 4.2, Dresden, 2007.
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52
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53349110750
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The delocalization index was calculated with the ToPMoD program on the basis of a single-point calculation performed with Gaussian 03:[16f] S. Noury, X. Krokidis, F. Fuster, B. Silvi, Program ToPMoD, Universite Pierre et Marie Curie, Paris, 2008
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[16f] S. Noury, X. Krokidis, F. Fuster, B. Silvi, Program ToPMoD, Universite Pierre et Marie Curie, Paris, 2008.
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53
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33751157179
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