ChemInform Abstract: Heavier Group 2 Grignard Reagents of the Type Aryl‐ae(L)n‐X (Post‐Grignard Reagents)

Westerhausen, Matthias; Langer, Jens; Krieck, Sven; Fischer, R.; Goerls, Helmar; Koehler, M.

doi:10.1002/chin.201423278

Cited by 3 publications

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“…As obvious as it might seem, very small changes in steric and electronic ligand properties can sometimes have dramatic consequences on the stabilization of a given type of complex. We report such a case in calcium chemistry where, despite the increasing interest and progress, [1][2][3][4][5] intriguing chemistry is still the norm.…”

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confidence: 99%

Highly fluorinated hydrotris(indazolyl)borate calcium complexes: the structure and reactivity heavily depend on the ligand's electronic properties

et al. 2014

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Two series of highly fluorinated 3-substituted hydrotris(indazolyl)borate (Fn-Tp(4Bo,3R); R = Ph, n = 12; R = CF3, n = 21) complexes of calcium were synthesized by salt metathesis reactions. CaI2 reacts with 2 and 1 equiv. of Tl(F12-Tp(4Bo,3Ph)) in THF to form the homo- and heteroleptic complexes [Ca(F12-Tp((4Bo,3Ph)*))2] (1) and [(F12-Tp(4Bo,3Ph))CaI(THF)] (2), respectively. 1 has C2h symmetry due to a 1,2-borotropic shift. The reaction of CaI2 with 2 equiv. of the more electron poor Tl(F21-Tp(4Bo,3CF3)) in THF, on the other hand, leads to the salt [Ca(THF)6][F21-Tp(4Bo,3CF3)]2 (3), with [F21-Tp(4Bo,3CF3)] acting as a counter-ion. This emphasizes the tuning ability of Fn-Tp(4Bo,3R) ligands and the consequences on their ability to bind hard electrophilic Ca(2+) centers.

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Section: Introductionmentioning

confidence: 99%

Highly fluorinated hydrotris(indazolyl)borate calcium complexes: the structure and reactivity heavily depend on the ligand's electronic properties

et al. 2014

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“…Over the last decade organometallic calcium, strontium and barium complexes have attracted some interest, [1][2][3] e.g. as precursors for metalorganic vapour deposition (MOCVD) 4,5 or as catalyst systems in polymerisation and hydrofunctionalization reactions.…”

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confidence: 99%

“…In this context, the η 5 -coordinate cyclopentadienyl ligand has played a prominent role in stabilizing half-sandwich and metallocene complexes. [10][11][12][13][14][15][16] More recently, these investigations have been extended to allyl systems, which can adopt both π-(η 3 ) and σ-(κC) bonding modes. [17][18][19][20][21][22][23][24][25] Pentadienyls, with their ability to adopt κC-, η 3 -and η 5 -coordination modes, occupy an intermediate position between the cyclopentadienyl and allyl systems, and their coordination chemistry with transition metals has been well established.…”

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confidence: 99%

“…Furthermore, the C-C distances within the pentadienyl system show a distinct short-long-long-shortpattern. Previous studies on [(η 5 -2,4-Me 2 C 5 H 5 ) 3 Nd], which also shows ionic bonding between the dienyl ligand and the metal cation, established that the M-C bonds to the formally a Two independent molecules in the asymmetric unit. b Pdl centroid is the centroid of the pentadienyl ligand.…”

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Pentadienyl chemistry of the heavy alkaline-earth metals revisited

et al. 2014

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Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

et al. 2016

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Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C 6 H 3 -2,6-(CH 2 PPh 2 ) 2 } 2 ] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo-(1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of tetrahydrofuran (THF) yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf) 3 Ca(X)(µ-O 2 PPh 2 )] 2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides (such as [(dme) 2 (thf)CaBr 2 ] (4)) form, supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

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ChemInform Abstract: Heavier Group 2 Grignard Reagents of the Type Aryl‐ae(L)n‐X (Post‐Grignard Reagents)

Cited by 3 publications

References 1 publication

Highly fluorinated hydrotris(indazolyl)borate calcium complexes: the structure and reactivity heavily depend on the ligand's electronic properties

Highly fluorinated hydrotris(indazolyl)borate calcium complexes: the structure and reactivity heavily depend on the ligand's electronic properties

Pentadienyl chemistry of the heavy alkaline-earth metals revisited

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

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