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Of most relevance to this study is the chemistry of Group 13-15 element(I) dimers, REER (R = bulky aryl, alkyl etc.,). For recent reviews in this area, see: a) E. Rivard, P. P. Power, Inorg. Chem. 2007, 46, 10047-10064;
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Note that intermolecular isopropyl hydride abstraction cannot be ruled out as contributing to the mechanism of formation of 18. Similar abstraction processes have been noted previously as giving rise to magnesium hydride complexes, see, for example: D. J. Gallagher, K. W. Henderson, A. R. Kennedy, C. T. O'Hara, R. E. Mulvey, R. B. Rowlings, Chem. Commun. 2002, 376-377
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Note that intermolecular isopropyl hydride abstraction cannot be ruled out as contributing to the mechanism of formation of 18. Similar abstraction processes have been noted previously as giving rise to magnesium hydride complexes, see, for example: D. J. Gallagher, K. W. Henderson, A. R. Kennedy, C. T. O'Hara, R. E. Mulvey, R. B. Rowlings, Chem. Commun. 2002, 376-377.
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Theoretical studies have predicted significantly shorter and stronger Be-Be bonds in compounds of the type RBeBeR (e.g, for R, Cp: Be-Be distances of ca. 2.06-2.08 Å; BDEs of ca. 70 kcalmol-1) than the Mg-Mg bonds of magnesium(I) dimers RMgMgR see Ref, 6
-
Theoretical studies have predicted significantly shorter and stronger Be-Be bonds in compounds of the type RBeBeR (e.g., for R = Cp: Be-Be distances of ca. 2.06-2.08 Å; BDEs of ca. 70 kcalmol-1) than the Mg-Mg bonds of magnesium(I) dimers RMgMgR (see Ref. [6]).
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62
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See the Supporting Information for further details
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See the Supporting Information for further details.
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84878609666
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-
Theoretical studies have predicted significantly longer and weaker Ca-Ca bonds in compounds of the type RCaCaR (Ca-Ca distances of ca. 3.73-3.82 Å; BDEs of < 30 kcal mol-1) than the Mg-Mg bonds of magnesium(I) dimers RMgMgR see Ref, 6
-
Theoretical studies have predicted significantly longer and weaker Ca-Ca bonds in compounds of the type RCaCaR (Ca-Ca distances of ca. 3.73-3.82 Å; BDEs of < 30 kcal mol-1) than the Mg-Mg bonds of magnesium(I) dimers RMgMgR (see Ref. [6]).
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-
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67
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51649102776
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The steric profiles of the ligands DippNacnac and tBuNacnac have previously been compared: P. L. Holland, Acc. Chem. Res. 2008, 41, 905-914.
-
The steric profiles of the ligands DippNacnac and tBuNacnac have previously been compared: P. L. Holland, Acc. Chem. Res. 2008, 41, 905-914.
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-
-
-
68
-
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37049077434
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-
The effect of the steric bulk of β-diketiminate ligands upon the planarity of their metallacyclic complexes has been previously noted, see, for example: P. B. Hitchcock, M. F. Lappert, D.-S. Liu, J. Chem. Soc. Chem. Commun. 1994, 1699-1700
-
The effect of the steric bulk of β-diketiminate ligands upon the planarity of their metallacyclic complexes has been previously noted, see, for example: P. B. Hitchcock, M. F. Lappert, D.-S. Liu, J. Chem. Soc. Chem. Commun. 1994, 1699-1700.
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-
-
-
69
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84878599587
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6]benzene after several days. A poor-quality crystal structure of the compound confirmed it to be monomeric in the solid state. No spectroscopic data were obtained. The mechanism of formation of this compound is unknown.
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6]benzene after several days. A poor-quality crystal structure of the compound confirmed it to be monomeric in the solid state. No spectroscopic data were obtained. The mechanism of formation of this compound is unknown.
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-
-
-
70
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84878592914
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The X-ray crystal structure of 21, although of low quality, ambiguously revealed the connectivity of the compound and showed it to have a similar geometry to that of 22.
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The X-ray crystal structure of 21, although of low quality, ambiguously revealed the connectivity of the compound and showed it to have a similar geometry to that of 22.
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-
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71
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33644500481
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L. F. Sánchez-Barba, D. L. Hughes, S. M. Humphrey, M. Bochmann, Organometallics 2006, 25, 1012-1020.
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Sánchez-Barba, L.F.1
Hughes, D.L.2
Humphrey, S.M.3
Bochmann, M.4
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72
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84878549909
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It is of note that the reduction of the unfunctionalized unsaturated substrate 1,3,5,7-cyclooctatetraene by 2 does occur, but only in toluene heated at reflux.
-
It is of note that the reduction of the unfunctionalized unsaturated substrate 1,3,5,7-cyclooctatetraene by 2 does occur, but only in toluene heated at reflux.
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-
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73
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0001192747
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It is of note that other magnesium reagents that can act as one electron reductants have been described. These include Mg/MgI2 mixtures, which have been proposed to be in equilibrium with univalent magnesium, Mgl, in solution. See, for example: M. D. Rausch, W. E. McEwen, J. Kleinberg, Chem. Rev. 1957, 57, 417, 437, and references therein
-
2 mixtures, which have been proposed to be in equilibrium with univalent magnesium, Mgl, in solution. See, for example: M. D. Rausch, W. E. McEwen, J. Kleinberg, Chem. Rev. 1957, 57, 417 - 437, and references therein.
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74
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84878537970
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It is of note that none of the magnesium(I) dimers 2, 16,or 17 react with the bulkier carbodiimide DippN = C=NDipp in toluene at 20 °C.
-
It is of note that none of the magnesium(I) dimers 2, 16,or 17 react with the bulkier carbodiimide DippN = C=NDipp in toluene at 20 °C.
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75
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43249098134
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Cowley, R.E.1
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Holland, P.L.6
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76
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0039811130
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See, for example: a
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See, for example: a) H. Zhou, H. Guo, Y. Yao, L. Zhou, H. Sun, H. Sheng, Y. Zhang, Q. Shen, Inorg. Chem. 2007, 46, 958-964;
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Zhou, H.1
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b) F. Yuan, Q. Shen, J. Sun, Polyhedron 1998, 17, 2009-2012.
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Bogdanovic, B.1
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n]: M. Michalczyk, Organometallics 1992, 11, 2307-2309.
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84
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2](R = amide, alkyl etc.,) had been previously prepared but not structurally characterized. See, for example : E. C. Ashby, A. B. Goel, Inorg. Chem. 1978, 17, 1862-1866.
-
2](R = amide, alkyl etc.,) had been previously prepared but not structurally characterized. See, for example : E. C. Ashby, A. B. Goel, Inorg. Chem. 1978, 17, 1862-1866.
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85
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84878540896
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2) has recently been described: M. Arrowsmith, M. S. Hill, D. J. MacDougall, M. F. Mahon, Angew. Chem. 2009, 121, 4073 - 4076;
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2) has recently been described: M. Arrowsmith, M. S. Hill, D. J. MacDougall, M. F. Mahon, Angew. Chem. 2009, 121, 4073 - 4076;
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2 in hexane at 50 °C for 20 min.
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2 in hexane at 50 °C for 20 min.
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G. M. Sheldrick, SHELXL97, Program for the Refinement of Crystal Structures, University of Göttingen, Göttingen (Germany), 1997.
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