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Volumn 16, Issue 3, 2010, Pages 938-955

β-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies

Author keywords

Low oxidation state; Magnesium; Magnesium hydrides; Metal metal interactions; X ray diffraction

Indexed keywords

ADDUCT FORMATION; ALL METAL; DENTICITY; DIKETIMINATES; HYDRIDE COMPLEXES; HYDRIDE LIGANDS; IODIDE COMPLEX; LEWIS BASIS; LOW OXIDATION STATE; LOW-YIELD; MAGNESIUM HYDRIDE; METAL-METAL INTERACTIONS; ORGANIC SUBSTRATE; STERIC BULK; STRUCTURAL AND PHYSICAL PROPERTIES; X RAY CRYSTAL STRUCTURES;

EID: 84878553170     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200902425     Document Type: Article
Times cited : (363)

References (96)
  • 1
    • 37249071800 scopus 로고    scopus 로고
    • 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;
    • 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;
  • 5
    • 0038578390 scopus 로고    scopus 로고
    • and references therein. See, for example
    • See, for example: S. Petrie, Aust. J. Chem. 2003, 56, 259 -262, and references therein.
    • (2003) Aust. J. Chem , vol.56 , pp. 259-262
    • Petrie, S.1
  • 7
    • 55249090179 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 8740-8744;
    • (2008) Angew. Chem. Int. Ed , vol.47 , pp. 8740-8744
  • 9
    • 85169614700 scopus 로고    scopus 로고
    • 5. See, for example : R. B. King, Polyhedron 2002, 21, 2347 -2350, and references therein.
    • 5. See, for example : R. B. King, Polyhedron 2002, 21, 2347 -2350, and references therein.
  • 12
    • 0001324599 scopus 로고    scopus 로고
    • Related magnesium(I) dimers, RMgMgX, have been proposed as intermediates in the formation of Grignard reagents, see, for example : P. G. Jasien, C. E. Dykstra, J. Am. Chem. Soc. 1983, 105, 2089-2090.
    • Related magnesium(I) dimers, RMgMgX, have been proposed as intermediates in the formation of Grignard reagents, see, for example : P. G. Jasien, C. E. Dykstra, J. Am. Chem. Soc. 1983, 105, 2089-2090.
  • 19
    • 33751211834 scopus 로고    scopus 로고
    • g)Q. S. Li, Y. Xu, J. Chem. Phys. 2006, 124-125, 11898-11902;
    • (2006) J. Chem. Phys , vol.124-125 , pp. 11898-11902
    • Li, Q.S.1    Xu, Y.2
  • 23
    • 53249115651 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 6526-6536;
    • (2008) Angew. Chem. Int. Ed , vol.47 , pp. 6526-6536
  • 28
    • 70349895675 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 5748 - 5751;
    • (2009) Angew. Chem. Int. Ed , vol.48 , pp. 5748-5751
  • 30
    • 58249124564 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 807-810;
    • (2009) Angew. Chem. Int. Ed , vol.48 , pp. 807-810
  • 35
    • 34447267419 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2007, 46, 4302-4305;
    • (2007) Angew. Chem. Int. Ed , vol.46 , pp. 4302-4305
  • 38
    • 33748542003 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 5807-5810;
    • (2006) Angew. Chem. Int. Ed , vol.45 , pp. 5807-5810
  • 42
    • 84878609497 scopus 로고    scopus 로고
    • M. Westerhausen, Angew. Chem. 2008, 120, 2215-2217; Angew. Chem. Int. Ed. 2008, 47, 2185-2187.
    • M. Westerhausen, Angew. Chem. 2008, 120, 2215-2217; Angew. Chem. Int. Ed. 2008, 47, 2185-2187.
  • 45
    • 56249147796 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 9079-9083.
    • (2008) Angew. Chem. Int. Ed , vol.47 , pp. 9079-9083
  • 48
    • 70349911694 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 2973 -2977.
    • (2009) Angew. Chem. Int. Ed , vol.48 , pp. 2973-2977
  • 52
    • 0004204702 scopus 로고
    • 2nd ed, Clarendon, Oxford
    • J. Emsley, The Elements, 2nd ed., Clarendon, Oxford, 1995.
    • (1995) The Elements
    • Emsley, J.1
  • 54
    • 75249104788 scopus 로고    scopus 로고
    • As determined from a survey of the Cambridge Crystallographic Database, August
    • As determined from a survey of the Cambridge Crystallographic Database, August, 2009.
    • (2009)
  • 57
    • 34250796829 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2007, 46, 2512-2514.
    • (2007) Angew. Chem. Int. Ed , vol.46 , pp. 2512-2514
  • 60
    • 0037148807 scopus 로고    scopus 로고
    • 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
    • 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.
  • 61
    • 84878598231 scopus 로고    scopus 로고
    • 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]).
  • 62
    • 84878534688 scopus 로고    scopus 로고
    • See the Supporting Information for further details
    • See the Supporting Information for further details.
  • 66
    • 84878609666 scopus 로고    scopus 로고
    • 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]).
  • 67
    • 51649102776 scopus 로고    scopus 로고
    • 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.
  • 68
    • 37049077434 scopus 로고    scopus 로고
    • 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.
  • 69
    • 84878599587 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 70
    • 84878592914 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 72
    • 84878549909 scopus 로고    scopus 로고
    • 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.
  • 73
    • 0001192747 scopus 로고    scopus 로고
    • 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.
  • 74
    • 84878537970 scopus 로고    scopus 로고
    • 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.
  • 82
    • 0025281552 scopus 로고
    • and references therein
    • Angew. Chem. Int. Ed. Engl. 1990, 29, 223-234, and references therein.
    • (1990) Angew. Chem. Int. Ed. Engl , vol.29 , pp. 223-234
  • 83
    • 33751392042 scopus 로고
    • n]: M. Michalczyk
    • n]: M. Michalczyk, Organometallics 1992, 11, 2307-2309.
    • (1992) Organometallics , vol.11 , pp. 2307-2309
  • 84
    • 0008544550 scopus 로고    scopus 로고
    • 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.
  • 85
    • 84878540896 scopus 로고    scopus 로고
    • 2) has recently been described: M. Arrowsmith, M. S. Hill, D. J. MacDougall, M. F. Mahon, Angew. Chem. 2009, 121, 4073 - 4076;
    • 2) has recently been described: M. Arrowsmith, M. S. Hill, D. J. MacDougall, M. F. Mahon, Angew. Chem. 2009, 121, 4073 - 4076;
  • 86
    • 70349783541 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 4013-4016.
    • (2009) Angew. Chem. Int. Ed , vol.48 , pp. 4013-4016
  • 87
    • 84878543627 scopus 로고    scopus 로고
    • 2 in hexane at 50 °C for 20 min.
    • 2 in hexane at 50 °C for 20 min.
  • 93
    • 84878621398 scopus 로고    scopus 로고
    • G. M. Sheldrick, SHELXL97, Program for the Refinement of Crystal Structures, University of Göttingen, Göttingen (Germany), 1997.
    • G. M. Sheldrick, SHELXL97, Program for the Refinement of Crystal Structures, University of Göttingen, Göttingen (Germany), 1997.


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