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(a) Paavola, S.; Zetterberg, K.; Privalov, T.; Csöregh, I.; Moberg, C. Adv. Synth. Catal. 2004, 346, 237-244.
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19
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0034678238
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and references therein
-
The ambidentate character of DMSO is quite remarkable. It has been demonstrated that the mode of DMSO coordination depends strongly on the interaction with the environment and by the effective electonegativity of the ligands coordinated to the metal center. See: Cotton, F. A.; Dikarev, E, V.; Petrukhina, M. A.; Striba, S.-E. Inorg. Chem. 2000, 39, 1748-1754, and references therein.
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Dikarev, E.V.2
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Striba, S.-E.4
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20
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0001608055
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2 both DMSO ligands are S-bond and the complex is dimeric with only one DMSO ligand at each end. See: (a) Bancroft, D. P.; Cotton, F. A.; Verbruggen, M. Acta Crystallogr. Sect. C 1989, 45, 1289-1292. However, the palladium(II) trifluoroacetate crystal structure has one S-bound and one O-bound DMSO.
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Acta Crystallogr. Sect. C
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Bancroft, D.P.1
Cotton, F.A.2
Verbruggen, M.3
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21
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0442303226
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See: (b) Stash, A. I.; Perepelkova, T. I.; Kravtsova, S. V.; Noskov, Yu. G.; Romm, I. P. Russ. J. Coord. Chem. 1998, 24, 36-39.
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22
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22944483170
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(c) Tanaka, D.; Romeril, S. P.; Myers. A, G. J. Am. Chem. Soc. 2005, 127, 10323-10333. Interestingly, X-ray crystallographic characterization of arylpalladium(II) trifluroacetates shows two S-bound DMSO ligands. See ref 5c. Palladium(II) trifluoroacetate structure was computationally evaluated and found in very good agreement with the X-ray crystal structure reported in ref 5c.
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Tanaka, D.1
Romeril, S.P.2
Myers, A.G.3
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23
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28944433251
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note
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2 is easy to verify directly within one geometry optimization sequence (see details in Supporting Information).
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-
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24
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28944435158
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PhenS = bathophenanthroline disulfonate, see ref 3e
-
PhenS = bathophenanthroline disulfonate, see ref 3e.
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-
-
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25
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28944444125
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note
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IiPr = 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazole; see ref 3h. Oxidation goes with added acid.
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26
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28944455181
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Private communication
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Stahl, S. Private communication.
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Stahl, S.1
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28
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11444250482
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(b) Stahl et al. has shown that in the case of palladium(0) complexes with nitrogen-based ligands spin crossover dynamics do not influence the overall oxygenation kinetics; see: Landis, C. R.; Morales, C. M.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 16302-16303.
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Stahl, S.S.3
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29
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28944431576
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note
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2 (2.15 Å).
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-
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30
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28944455419
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note
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Geometry optimization of the Pd(0) with up to eight DMSO ligands was carried out in the gas phase and solvent (PCM). The first coordination sphere of Pd(0) could hold only four sulfur-bonded DMSO; additional ligands were weakly coordinated in the second coordination sphere.
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31
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28944449505
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note
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10 electron configuration of Pd(0) every d orbital is doubly occupied. Symmetric electron distribution means that there are no ligand field effects and the ligand positions are sterically determined.
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32
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28944432707
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note
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This effect is well known in physical organic chemistry and is called hyperconjugation.
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33
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28944452882
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note
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Hydrogen bonding is characterized by the elongation of the X-H bond, a decrease of its stretch frequency, and an increase of intensity of the respective spectral band. An increase of ED in the σ* orbital is accompanied by weakening of the corresponding bond and its elongation and a concomitant lowering of the X-H stretch frequency.
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35
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0345491105
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(b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
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(b) Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; Defrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665.
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Stratmann, R.E.9
Burant, J.C.10
Dapprich, S.11
Millam, J.M.12
Daniels, A.D.13
Kudin, K.N.14
Strain, M.C.15
Farkas, O.16
Tomasi, J.17
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Cammi, R.20
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Pomelli, C.22
Adamo, C.23
Clifford, S.24
Ochterski, J.25
Petersson, G.A.26
Ayala, P.Y.27
Cui, Q.28
Morokuma, K.29
Malick, D.K.30
Rabuck, A.D.31
Raghavachari, K.32
Foresman, J.B.33
Cioslowski, J.34
Ortiz, J.V.35
Baboul, A.G.36
Stefanov, B.B.37
Liu, G.38
Liashenko, G.39
Piskorz, P.40
Komaromi, I.41
Gomperts, R.42
Martin, R.L.43
Fox, D.J.44
Keith, T.45
Al-Laham, M.A.46
Peng, C.Y.47
Nanayakkara, A.48
Challacombe, M.49
Gill, P.M.W.50
Johnson, B.51
Chen, W.52
Wong, M.W.53
Andres, J.L.54
Gonzalez, C.55
Head-Gordon, M.56
Replogle, E.S.57
Pople, J.A.58
more..
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42
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28944454211
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note
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The use of the effective potential LanL2DZ basis set for thermochemical analysis, namely, for acquiring thermodynamic functions and Gibbs free energy, has regularly been found to result in a level of accuracy comparable to that of superior basis sets to a small fraction of computational costs.
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