Intramolekulare C‐H‐Aktivierung in Erdalkalimetall‐Komplexen

Harder, Sjoerd

doi:10.1002/ange.200351055

Cited by 32 publications

(19 citation statements)

References 52 publications

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“…[2a,2b,3d-3h,16] The structures of 1-3 are shown in Figures 1, 2, and 3, respectively, and clearly prove such a coordination mode. (12), Bi(1)-Cl(2) 2.8513 (12), Bi(1)-Cl(2A) 2.8720(15), C(1)-C(2) 1.510(6), C(2)-C(3) 1.398(5), C(3)-C(4) 1.411 (5), C(4)-C(5) 1.505 (5), C(2)-N(1) 1.349 (5), C(4)-N(2) 1.335 (5); N(1)-Bi(1)-N(2) 83.40 (11), N(1)-Bi(1)-Cl (1) [14b] Noteworthy features in 1-3 are the stereochemically active geometries of the nonbonding lone pair around the Bi III centers, which are suggested to fit the 10-Bi-4 and 12-Bi-5 systems (n-Bi-l, where n is number of formal valence-shell electrons about a Bi atom and l is the number of ligands) predicted by simple valence-shell electron-pair repulsion theory. [18] Thus, square-pyramidal geometry was adopted for each five-coordinate Bi center, and triangular-pyramidal geometry was adopted for each fourcoordinate Bi center, in which some degrees of geometric distortion were observed from the ideal polyhedra, probably due to the different ligation groups at the metal centers.…”

Section: Resultsmentioning

confidence: 99%

“…[10a,10c] In other main-group compounds several other coordination features are also observed. [11][12][13] This indicates a rich coordination chemistry of group 15 elements has not been reached, and the reaction mechanisms still remain speculative, although many experiments have been investigated, which include the use of different precursors and changing the reaction and/or isolation conditions. [7b,7c] Moreover, As and Bi complexes of L are unknown to date.…”

Section: Introductionmentioning

confidence: 99%

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The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

Zhu

Tan

et al. 2011

Eur J Inorg Chem

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The reaction of BiCl3 with LLi {L = HC[(CMe)(NAr)]2, Ar = 2,6‐iPr2C6H3} in a molar ratio of 1:1 was carried out under various conditions and afforded [LBiCl(μ‐Cl)]2 (1), [L′BiCl(μ‐Cl)]2 [4; L′ = N(Ar)=C(Me)CH=C(NHAr)CH2], and L″Bi2Cl4 [5; L″ = N(Ar)=C(Me)CC(Me)=N(Ar)]. Compounds 1 and 4 are isomers, and a thermal conversion of 1 to 4 was realized. In this reaction system, when a little excess nBuLi and BiCl3 were used, [LBiCl(μ‐Cl)Bi(nBu)Cl(μ‐Cl)]2 (2) was isolated as side product after the isolation of 1. The reaction of 1 with AgOOCCF3 in the absence of light from –15 °C to room temperature generated LBi(OOCCF3)2 (3). Finally, the solvent‐free reaction of BiCl3 and LH at elevated temperature (125 °C) under vacuum gave [LH2]+[BiCl4(THF)]– (6) in a low yield. The formulations of all these complexes have been confirmed by 1H and 13C NMR spectroscopy and X‐ray crystallography, except for 6, which was only identified by X‐ray crystallography due to its insolubility in organic solvents. These complexes exhibit versatile L ligation modes at the metal atom and reveal the complexity of the reaction between BiCl3 and LLi.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

Zhu

Tan

et al. 2011

Eur J Inorg Chem

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“…The mesomerism of picolyl anions has been described previously and aza-allyl coordination by a doubly-activated b-diketiminato ligand to calcium has been discussed. [28,29] Figure 1 depicts a formally seven-coordinate calcium center. The bond lengths of 2.846(3) (Ca1-C6) and 2.813(3) (Ca1-C13) lie in the range of calcium-carbon bonds observed for the triglyme adduct of bisA C H T U N G T R E N N U N G (h 3 -allyl)calcium and exclude s-bound carbanionic ligands.…”

mentioning

confidence: 99%

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Jochmann

Leich

Spaniol

et al. 2011

Chemistry A European J

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A facile and general synthetic pathway for the production of dearomatized, allylated, and C-H bond activated pyridine derivatives is presented. Reaction of the corresponding derivative with the previously reported reagent bis(allyl)calcium, [Ca(C(3)H(5))(2)] (1), cleanly affords the product in high yield. The range of N-heterocyclic compounds studied comprised 2-picoline (2), 4-picoline (3), 2,6-lutidine (4), 4-tert-butylpyridine (5), 2,2'-bipyridine (6), acridine (7), quinoline (8), and isoquinoline (9). Depending on the substitution pattern of the pyridine derivative, either carbometalation or C-H bond activation products are obtained. In the absence of methyl groups ortho or para to the nitrogen atom, carbometalation leads to dearomatized products. C(sp(3))-H bond activation occurs at ortho and para situated methyl groups. Steric shielding of the 4-position in pyridine yields the ring-metalated product through C(sp(2))-H bond activation instead. The isolated compounds [Ca(2-CH(2)-C(5)H(4)N)(2)(THF)] (2b⋅(THF)), [Ca(4-CH(2)-C(5)H(4)N)(2)(THF)(2)] (3b⋅(THF)(2)), [Ca(2-CH(2)-C(5)H(3)N-6-CH(3))(2)(THF)(n)] (4b⋅(THF)(n); n=0, 0.75), [Ca{2-C(5)H(3)N-4-C(CH(3))(3)}(2)(THF)(2)] (5c⋅(THF)(2)), [Ca{4,4'-(C(3)H(5))(2)-(C(10)H(8)N(2))}(THF)] (6a⋅(THF)), [Ca(NC(13) H(9)-9-C(3)H(5))(2)(THF)] (7a⋅(THF)), [Ca(4-C(3) H(5)-C(9) H(7)N)(2)(THF)] (8b⋅(THF)), and [Ca(1-C(3)H(5)-C(9)H(7) N)(2)(THF)(3)] (9a⋅(THF)(3)) have been characterized by NMR spectroscopy and metal analysis. 9a⋅(THF)(4) and 4b⋅(THF)(3) were additionally characterized in the solid state by X-ray diffraction experiments. 4b⋅(THF)(3) shows an aza-allyl coordination mode in the solid state. Based on the results, mechanistic aspects are discussed in the context of previous findings.

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“…They can play a role in redox reactions, [13] act as nucleophiles [14] or electrophiles, [15] and react as an acid [16] or a base. [17] A similar protonation of the b-diketiminate ligand has been…”

Section: Thermal Decomposition Of Ca(dippmentioning

confidence: 99%

Calcium–Amidoborane–Ammine Complexes: Thermal Decomposition of Model Systems

Harder¹,

Spielmann

Tobey

2012

Chemistry A European J

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Hydrocarbon-soluble model systems for the calcium-amidoborane-ammine complex Ca(NH(2)BH(3))(2)⋅(NH(3))(2) were prepared and structurally characterized. The following complexes were obtained by the reaction of RNH(2)BH(3) (R = H, Me, iPr, DIPP; DIPP = 2,6-diisopropylphenyl) with Ca(DIPP-nacnac)(NH(2))⋅(NH(3))(2) (DIPP-nacnac = DIPP-NC(Me)CHC(Me)N-DIPP): Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))(2), Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))(3), Ca(DIPP-nacnac)[NH(Me)BH(3)]⋅(NH(3))(2), Ca(DIPP-nacnac)[NH(iPr)BH(3)]⋅(NH(3))(2), and Ca(DIPP-nacnac)[NH(DIPP)BH(3)]⋅NH(3). The crystal structure of Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3)(3) showed a NH(2)BH(3)(-) unit that was fully embedded in a network of BH⋅⋅⋅HN interactions (range: 1.97(4)-2.39(4) Å) that were mainly found between NH(3) ligands and BH(3) groups. In addition, there were N-H⋅⋅⋅C interactions between NH(3) ligands and the central carbon atom in the ligand. Solutions of these calcium-amidoborane-ammine complexes in benzene were heated stepwise to 60 °C and thermally decomposed. The following main conclusions can be drawn: 1) Competing protonation of the DIPP-nacnac anion by NH(3) was observed; 2) The NH(3) ligands were bound loosely to the Ca(2+) ions and were partially eliminated upon heating. Crystal structures of [Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))](∞), Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))⋅(THF), and [Ca(DIPP-nacnac){NH(iPr)BH(3)}](2) were obtained. 3) Independent of the nature of the substituent R in NH(R)BH(3), the formation of H(2) was observed at around 50 °C. 4) In all cases, the complex [Ca(DIPP-nacnac)(NH(2))](2) was formed as a major product of thermal decomposition, and its dimeric nature was confirmed by single-crystal analysis. We proposed that thermal decomposition of calcium-amidoborane-ammine complexes goes through an intermediate calcium-hydride-ammine complex which eliminates hydrogen and [Ca(DIPP-nacnac)(NH(2))](2). It is likely that the formation of metal amides is also an important reaction pathway for the decomposition of metal-amidoborane-ammine complexes in the solid state.

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Intramolekulare C‐H‐Aktivierung in Erdalkalimetall‐Komplexen

Cited by 32 publications

References 52 publications

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Calcium–Amidoborane–Ammine Complexes: Thermal Decomposition of Model Systems

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Intramolekulare C‐H‐Aktivierung in Erdalkalimetall‐Komplexen

Cited by 32 publications

References 52 publications

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]2 {L = HC[(CMe)(NAr)]2, Ar = 2,6‐iPr2C6H3} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]2 {L = HC[(CMe)(NAr)]2, Ar = 2,6‐iPr2C6H3} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Calcium–Amidoborane–Ammine Complexes: Thermal Decomposition of Model Systems

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The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]₂ {L = HC[(CMe)(NAr)]₂, Ar = 2,6‐iPr₂C₆H₃} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes