Stereoselective Enolizations Mediated by Magnesium and Calcium Bisamides: Contrasting Aggregation Behavior in Solution and in the Solid State

He, Xuyang; Allan, John F.; Noll, Bruce C.; Kennedy, Aileen; Henderson, Kenneth W.

doi:10.1021/ja051050c

Cited by 48 publications

(58 citation statements)

References 18 publications

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“…In this case, 10 is initially precipitated and the small amount of residual 3 remains in solution. 50 but it differs from the η 1 bonding mode of toluene in [Er(η 2 -3,5-di-tert-butyl pyrazolate) 4 ][K(18-crown-6)-(DME)(toluene)]. 51 This suggests that the presence of monodentate THF or bidentate toluene versus bidentate DME on one side of the crown ether can influence toluene coordination on the other side.…”

Section: Resultsmentioning

confidence: 99%

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺

et al. 2011

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New syntheses of complexes containing the recently discovered (N(2))(3-) radical trianion have been developed by examining variations on the LnA(3)/M reductive system that delivers "LnA(2)" reactivity when Ln = scandium, yttrium, or a lanthanide, M = an alkali metal, and A = N(SiMe(3))(2) and C(5)R(5). The first examples of LnA(3)/M reduction of dinitrogen with aryloxide ligands (A = OC(6)R(5)) are reported: the combination of Dy(OAr)(3) (OAr = OC(6)H(3)(t)Bu(2)-2,6) with KC(8) under dinitrogen was found to produce both (N(2))(2-) and (N(2))(3-) products, [(ArO)(2)Dy(THF)(2)](2)(μ-η(2):η(2)-N(2)), 1, and [(ArO)(2)Dy(THF)](2)(μ-η(2):η(2)-N(2))[K(THF)(6)], 2a, respectively. The range of metals that form (N(2))(3-) complexes with [N(SiMe(3))(2)](-) ancillary ligands has been expanded from Y to Lu, Er, and La. Ln[N(SiMe(3))(2)](3)/M reactions with M = Na as well as KC(8) are reported. Reduction of the isolated (N(2))(2-) complex {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2)), 3, with KC(8) forms the (N(2))(3-) complex, {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)], 4a, in high yield. The reverse transformation, the conversion of 4a to 3 can be accomplished cleanly with elemental Hg. The crown ether derivative {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2))[K(18-crown-6)(THF)(2)] was isolated from reduction of 3 with KC(8) in the presence of 18-crown-6 and found to be much less soluble in tetrahydrofuran (THF) than the [K(THF)(6)](+) salt, which facilitates its separation from 3. Evidence for ligand metalation in the Y[N(SiMe(3))(2)](3)/KC(8) reaction was obtained through the crystal structure of the metallacyclic complex {[(Me(3)Si)(2)N](2)Y[CH(2)Si(Me(2))NSiMe(3)]}[K(18-crown-6)(THF)(toluene)]. Density functional theory previously used only with reduced dinitrogen complexes of closed shell Sc(3+) and Y(3+) was extended to Lu(3+) as well as to open shell 4f(9) Dy(3+) complexes to allow the first comparison of bonding between these four metals.

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Section: Resultsmentioning

confidence: 99%

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺

et al. 2011

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“…Alkali-alkaline earth mixed metal amides have solubility in organic solvents and unique reactivity that is markedly different from that of a mixture of the homometallic counterparts [125][126][127][128][129][130][131][132]. Alkaline earth-alkaline earth mixed metal species are less well known and limited to [MgCa{N(SiMe 3 ) 2 } 4 ] [127].…”

Section: Alkaline Earth Heterobimetallic Amidesmentioning

confidence: 99%

Advances in alkaline earth-nitrogen chemistry

Torvisco

O'Brien

Ruhlandt‐Senge

2011

Coordination Chemistry Reviews

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“…Solutions of calcium dienolate ([Ca(OR) 2 ]) and calcium diamide ([Ca(NRR 1 ) 2 ]) contain also the mixed complex ([Ca(OR)(NRR 1 )]) 73 , and therefore, presumably their Gibbs free energy differences are small. The calcium enolates in this study are monomeric and their magnesium analogues are dimeric.…”

Section: Group 2: Beryllium Magnesium Calcium Strontium and Bmentioning

confidence: 99%

Thermochemical Considerations of Metal Enolates

Liebman

Slayden

2010

Patai's Chemistry of Functional Groups

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Introduction Group 1: Lithium, Sodium, Potassium, Rubidium and Cesium Group 2: Beryllium, Magnesium, Calcium, Strontium and Barium Group 13: Aluminum, Gallium, Indium and Thallium Group 14: Tin and Lead Group 11: Copper, Silver and Gold Group 12: Zinc, Cadmium and Mercury Group 3: Scandium, Yttrium and the Lanthanides Actinides Group 4: Titanium, Zirconium and Hafnium Group 5: Vanadium, Niobium and Tantalum Group 6: Chromium, Molybdenum and Tungsten Group 7: Manganese and Rhenium Group 8: Iron, Ruthenium and Osmium Group 9: Cobalt, Rhodium and Iridium Group 10: Nickel, Palladium and Platinum

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Stereoselective Enolizations Mediated by Magnesium and Calcium Bisamides: Contrasting Aggregation Behavior in Solution and in the Solid State

Cited by 48 publications

References 18 publications

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺

Advances in alkaline earth-nitrogen chemistry

Thermochemical Considerations of Metal Enolates

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Stereoselective Enolizations Mediated by Magnesium and Calcium Bisamides: Contrasting Aggregation Behavior in Solution and in the Solid State

Cited by 48 publications

References 18 publications

(N2)3− Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N2)2− and (N2)3− Complexes and Density Functional Theory Comparisons of Closed Shell Sc3+, Y3+, and Lu3+ versus 4f9 Dy3+

(N2)3− Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N2)2− and (N2)3− Complexes and Density Functional Theory Comparisons of Closed Shell Sc3+, Y3+, and Lu3+ versus 4f9 Dy3+

Advances in alkaline earth-nitrogen chemistry

Thermochemical Considerations of Metal Enolates

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Product

Resources

About

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺

(N₂)³⁻ Radical Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of Dinitrogen: New Syntheses and Examples of (N₂)²⁻ and (N₂)³⁻ Complexes and Density Functional Theory Comparisons of Closed Shell Sc³⁺, Y³⁺, and Lu³⁺ versus 4f⁹ Dy³⁺