Stable “Inverse” Sandwich Complex with Unprecedented Organocalcium(I): Crystal Structures of [(thf)2Mg(Br)-C6H2-2,4,6-Ph3] and [(thf)3Ca{μ-C6H3-1,3,5-Ph3}Ca(thf)3]

Krieck, Sven; Görls, Helmar; Yu, Lian; Reiher, Markus; Westerhausen, Matthias

doi:10.1021/ja808524y

Cited by 166 publications

(159 citation statements)

References 75 publications

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“…[5,6] Presumably, this is a result of the bidentate b-diketiminates that were employed in that work, which were not able to supply adequate steric and/or electronic protection to the metal centers of the target complexes. It occurred to us that if sufficiently bulky tris(pyrazolyl)methanides could be developed, these ligands may allow access to group 2 metal(I) dimers and related kinetically labile systems.…”

Section: Introductionmentioning

confidence: 99%

An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes

Lalrempuia

Stasch

Jones

2014

Chemistry An Asian Journal

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The tris(pyrazolyl)methane compound HC(3-Ad-5-Mepz)3 [1, 3-Ad-5-Mepz=3-(1-adamantyl)-5-methylpyrazolyl] and its regioisomer, HC(3-Ad-5-Mepz)2 (3-Me-5-Adpz), were synthesized and crystallographically characterized. Deprotonation of 1 with MeLi afforded the lithium complex [{κ(3) -N-C(3-Ad-5-Mepz)3 }Li(thf)], which incorporates a tris(pyrazolyl)methanide ligand of unprecedented bulk. Reaction of 1 with MeMgI gave the ionic coordination complex [{κ(3) -N-HC(3-Ad-5-Mepz)3 }MgMe]I, which was readily deprotonated to afford the neutral compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgMe]. The related magnesium butyl compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgBu] was prepared from the reaction of 1 and MgBu2 . Treating this with LiAlH4 or LiAlD4 led to rare examples of terminal magnesium hydride/deuteride complexes, [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgH/D]. All neutral magnesium alkyl and hydride compounds were crystallographically authenticated. Reaction of [{κ(3) κN-C(3-Ad-5-Mepz)3 }Li(thf)] with [YbI2 (thf)2 ] yielded the first structurally characterized f-block tris(pyrazolyl)methanide complex, [{κ(3) -N-C(3-Ad-5-Mepz)3 }YbI(thf)].

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Section: Introductionmentioning

confidence: 99%

An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes

Lalrempuia

Stasch

Jones

2014

Chemistry An Asian Journal

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“…With some recent remarkable exceptions (Green et al 2007(Green et al , 2008Bonyhady et al 2009;Krieck et al 2009), the organometallic compounds of the heavy alkaline earths are overwhelmingly redox inactive species, which demonstrate a +2 oxidation state. The M 2+ cations achieve noble gas configurations, and compounds of the heavy metals possess a d 0 electron configuration.…”

Section: Introductionmentioning

confidence: 99%

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

et al. 2010

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Despite the routine employment of Grignard reagents and Hauser bases as stoichiometric carbanion reagents in organic and inorganic synthesis, a defined reaction chemistry encompassing the heavier elements of Group II (M = Ca, Sr and Ba) has, until recently, remained unreported. This article provides details of the recent progress in heavier Group II catalysed small molecule transformations mediated by well-defined heteroleptic and homoleptic complexes of the form LMX or MX 2 ; where L is a mono-anionic ligand and X is a reactive s-bonded substituent. The intra-and intermolecular heterofunctionalization (hydroamination, hydrophosphination, hydrosilylation and hydrogenation) of alkenes, alkynes, dienes, carbodiimides, isocyanates and ketones is discussed.

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“…[8] A few years ago, his research group began an ongoing study of the calcium analogues of Grignard reagents. The first compounds to be made were phenyl (or monosubstituted phenyl) derivatives that were referred to in 1905, but inadequately characterized.…”

Section: Theorganometallicchemistryofthes-blockelements-frommentioning

confidence: 99%

“…This article highlights examples from two of the leading research groups in this area. [7,8] In each case, the compounds of the heavier elements differ from those of the lighter congeners, and show how changes in the size of the metals determine the structures of their organometallic compounds.The synthetic potential of methandiides (R 2 CM 2 ) has long been recognized, [9] but few have been isolated. The dimeric compounds [{[Ph 2 P(NSiMe 3 )] 2 C} 2 M 4 ] (M = Li, 1; Scheme 1), were obtained by the research groups of Cavell [10] and Stephan [11] 10 years ago.…”

mentioning

confidence: 99%

Organometallic Compounds of the Heavier s‐Block Elements—What Next?

Smith

2009

Angew Chem Int Ed

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alkali metals · alkaline earth metals · coordination modes · methandiides · organometallic compoundsTheorganometallicchemistryofthes-blockelements-from its origins 150 years ago to the present day-was recently reviewed in two fascinating essays. [1,2] Organolithium and Grignard reagents, now often bought in solution, have been used routinely in organic syntheses for many years. In contrast, much less is known about the potential, in synthesis or catalysis, of organometallic compounds of the heavier sblock elements. In part, this neglect is a natural consequence of the attention paid to compounds of the lighter elements, but development has also been held back by the simplistic view given in some textbooks that, whereas LiÀC and MgÀC bonds are covalent, KÀC and CaÀC bonds are ionic. The carbanions associated with the metal cations are, therefore, powerful nucleophiles that deprotonate ether solvents. This has made synthesis difficult and discouraged investigation.The applications of organolithium and Grignard-type reagents have been greatly expanded by the development of so-called "superbases", that is, compounds containing two different metals, [2,3] but what of the organometallic compounds of individual heavier s-block elements in the absence of lighter atoms? A variety of alkali-metal compounds have been known for some time, [4] but it is only recently that researchers have made significant progress in exploring the chemistry of the organometallic compounds of the heavier alkaline earth metals.[5] As in organolithium compounds, [6] the bonding in all these compounds is highly ionic, but when the nucleophilicity of the carbanion is reduced by extensive delocalization of the negative charge on to bulky aryl, bdiketiminato or silicon-containing ligands, a range of compounds can be isolated. It is clear that these do not simply provide a minor variation on what is already known about the lighter elements. Unexpected reactions and unprecedented structures point to exciting new chemistry. This article highlights examples from two of the leading research groups in this area. [7,8] In each case, the compounds of the heavier elements differ from those of the lighter congeners, and show how changes in the size of the metals determine the structures of their organometallic compounds.The synthetic potential of methandiides (R 2 CM 2 ) has long been recognized, [9] but few have been isolated. The dimeric compounds [{[Ph 2 P(NSiMe 3 )] 2 C} 2 M 4 ] (M = Li, 1; Scheme 1), were obtained by the research groups of Cavell [10] and Stephan [11] 10 years ago. Further dimers in which M

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Stable “Inverse” Sandwich Complex with Unprecedented Organocalcium(I): Crystal Structures of [(thf)₂Mg(Br)-C₆H₂-2,4,6-Ph₃] and [(thf)₃Ca{μ-C₆H₃-1,3,5-Ph₃}Ca(thf)₃]

Cited by 166 publications

References 75 publications

An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes

An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

Organometallic Compounds of the Heavier s‐Block Elements—What Next?

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