(Dioxane)dineopentylmagnesium: a polymeric structure

Parvez, Masood; Pajerski, Anthony D.; Richey, Herman G.

doi:10.1107/s0108270188003099

Cited by 11 publications

(7 citation statements)

References 7 publications

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“…However, the connectivity that was established is shown in Figure . Similar structures also have been observed for [(μ-diox- O , O ′)Mg(CH 2 t Bu) 2 ] ∞ , [(μ-diox- O , O ′)MgPh 2 ] ∞ , and [(μ-diox- O , O ′)MgEt 2 ] ∞ …”

Section: Resultssupporting

confidence: 80%

“…While the addition of 1,4-dioxane to diethyl ether solutions of Grignard reagents results in precipitation of [(μ-diox)MgX 2 ] ∞ and [(μ-diox)Mg(R)X] ∞ , , [(μ-diox)MgR 2 ] ∞ also precipitates, when a 1:1 dioxane to magnesium ratio is used. , The addition of further dioxane leads to partial cleavage of the [(μ-diox)MgR 2 ] ∞ polymer chain into smaller fragments, making the R 2 Mg component soluble while the dihalide species remain insoluble. If [(μ-diox)Mg(R)X] ∞ has a higher solubility than [(μ-diox)MgX 2 ] ∞ in the presence of an excess of dioxane, it disproportionates via the Schlenk equilibrium to insoluble magnesium dihalide and soluble [(diox) n +1 (MgR 2 ) n ] .…”

Section: Resultsmentioning

confidence: 99%

“…However, there have been very few structural investigations of dioxane adducts of organomagnesium compounds. The known examples showed that this bidentate cyclic ether can act as a monodentate ligand, as in the carborate [(diox) 2 Mg(2-Me-1,2-C 2 B 10 H 10 ) 2 ], and as a bridging ligand, as in polymeric [(diox)Mg(CH 2 t Bu) 2 ] ∞ and in the related molecular magnesium amide [(R 2 N) 2 Mg(μ-diox)Mg(NR 2 ) 2 ] with three-coordinate magnesium atoms (R = SiMe 3 )…”

Section: Introductionmentioning

confidence: 99%

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1,4-Dioxane Adducts of Grignard Reagents: Synthesis, Ether Fragmentation Reactions, and Structural Diversity of Grignard Reagent/1,4-Dioxane Complexes

et al. 2009

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The 1,4-dioxane precipitation method was employed to obtain solutions of R 2 Mg from Grignard reagents via precipitation of polymeric magnesium dihalides as dioxane adducts. The addition of a slight excess of dioxane resulted in partial cleavage of the initially formed [( μ-diox)MgR 2 ] ¥ polymer into smaller fragments of the type [(diox) nþ1 (MgR 2 ) n ]. In addition to the polymeric compounds(2) can be obtained from such solutions. In the system MesMgBr/1,4dioxane the compounds [( μ-diox)MgBr 2 ] ¥ and [( μ-diox)Mg(Mes) 2 ] ¥ are both sparingly soluble, offering the opportunity to remove most of these compounds from the reaction mixture and leaving the products of ether cleavage reactions as the major species in solution. Using this procedure, the new ether degradation products [(diox)Mg(Mes)(μ-OEt)] 2 (3) and [(EtOCH(Me)CH(Me)OEt)Mg-(Mes) 2 ] (4) were isolated. Excess dioxane yields mononuclear [(diox) 2 Mg(Mes) 2 ] (5). Exchange of the thf coligands in closely related [(thf) 2 Mg(Mes) 2 ] for other Lewis bases such as 2,2 0 -bipyridine (bpy) and 2,4,6-trimethylphenyl (Mes) anions allowed the preparation of [(bpy)Mg(Mes) 2 ] (6) and [(thf) 4 -Li] þ [Mg(Mes) 3 ] -(7). Molecular structures of all new compounds 2-7 are reported.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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1,4-Dioxane Adducts of Grignard Reagents: Synthesis, Ether Fragmentation Reactions, and Structural Diversity of Grignard Reagent/1,4-Dioxane Complexes

et al. 2009

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“…This structure represents the first crystallographically characterized example of this important utility bis-alkyl magnesium species, the closest structure obtained thus far being TMEDA solvated s Bu 2 Mg, which crystallized preferentially from a solution of 'Bu 2 Mg' containing both n Bu and s Bu ligands. 25 Other similar examples include a dioxane bridged polymer of neo Pe 2 Mg, 26 Having 'trapped' a tetranuclear fragment of presumably polymeric n Bu 2 Mg, the ratio of starting materials was altered to 1 : 4 in an attempt to obtain a longer bis-alkyl magnesium chain. However, the resulting product was shown by 1 H NMR spectroscopy and comparison of its unit cell parameters to indeed be 4, suggesting that this tetranuclear structure is produced regardless of the ratio of the starting materials.…”

Section: Synthesis and Solid State Structure Of Bisalkyl Magnesium Ca...mentioning

confidence: 99%

N-Heterocyclic carbene stabilized adducts of alkyl magnesium amide, bisalkyl magnesium and Grignard reagents: trapping oligomeric organo s-block fragments with NHCs

2010

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Developing N-heterocyclic carbene (NHC) chemistry of simple organomagnesium compounds, this study reports the synthesis, X-ray crystallographic, and NMR spectroscopic characterization of three such new carbene complexes. The 1 : 1 alkyl magnesium amide : carbene complexes nBuMg(TMP)·IPr 1 and nBuMg(HMDS)·IPr 2 both exist as mononuclear complexes in the crystal but differ in solution as 2 remains intact whereas 1 undergoes a dynamic exchange involving partial decoordination of IPr [TMP is 2,2,6,6-tetramethylpiperidide; IPr is 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene); HMDS is 1,1,1,3,3,3-hexamethyldisilazide]. Reaction of commercial nBu(2)Mg with IPr surprisingly produced the organoaluminium carbene complex nBu(3)Al·IPr, 3, which also forms a simple mononuclear structure in the crystal. The presence of the Al could be traced to the deliberate addition of a small quantity of Et(3)Al as a stabilizing agent in the commercial nBu(2)Mg reagent. Repeating this reaction with Al-free nBu(2)Mg afforded the hemisolvated carbene complex nBu(8)Mg(4)·2IPr, 4, the stoichiometry of which is dictated by its structure rather than by that used in the initial reaction mixture. The molecular structure of 4 is tetranuclear with a linear chain of 4 Mg centres bridged by nBu ligands and capped at each end by terminal nBu and IPr ligands. Synthesized by treating the Grignard reagent nBuMgCl with IPr, nBuMgCl·IPr, 5, forms a cyclodimer structure with chloro bridges and terminal nBu and IPr ligands.

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“…Besides mononuclear complexes of the type [R 2 Mg(η 1 ‐dx) 2 ] ( 2‐R with R=Mes, 2‐MeC 2 B 10 H 10 , and C 9 H 7 (indenyl)), dinuclear congeners [{R 2 Mg(dx)} 2 (μ‐dx)] (type 1.5‐R with R=Bz) have also been investigated. Strand‐like structures such as [R 2 Mg(μ‐dx)] ∞ (type 1′‐R with R=Et, CH 2 t Bu, i Pr, Ph, Cy, and Cp) with bridging dioxane ligands are observed in most cases in the crystalline state. The mononuclear silanide complex [{(Me 3 Si) 2 MeSi} 2 Mg(dx) 2 ] of type 2 , the strand‐like magnesiate [LiMg(CH 2 SiMe 3 ) 3 (μ‐dx)(η 1 ‐dx)] ∞ , and the tetranuclear heteroscorpionate complex [{L(MgCH 2 SiMe 3 ) 2 } 2 (μ‐dx)] expand this class of dioxane adducts .…”

Section: Introductionmentioning

confidence: 99%

Structure–Solubility Relationship of 1,4‐Dioxane Complexes of Di(hydrocarbyl)magnesium

Fischer

Görls

Meisinger

et al. 2019

Chemistry A European J

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Systematic variation of the 1,4-dioxane (dx) concentration during the precipitation of sparingly soluble [MgBr 2 (dx) 2 ] from ethereal Grignard solutions of RMgBr has allowed the structural investigation of crystallized [R 2 Mg(dx) n ] (n = 1, 1.5, 2, and 3), which form during this dioxane method, depending on the bulkiness of R. The numbering of the complexes explored in this study is based on the number n of dioxane molecules per magnesium atom, followed by the substituent R; an apostrophe denotes coordination polymers. The following derivatives were studied by X-ray crystal-structure determination and NMR spectroscopy :(1.5-oTol), and [(Me 3 Si-CC) 2 Mg(dx) 1.5 ] 1 (1.5'-C 2 SiMe 3 ); n = 2: [tBu 2 Mg(dx) 2 ] (2-tBu) and [oTol 2 Mg(dx) 2 ] (2-oTol); n = 3: [Ph 2 Mg(dx) 3 ] (3-Ph). In the structure types 1', 1.5, and 2, the magnesium atom exhibits the coordination number 4, whereas pentacoordinate metal atoms are observed in types 3 and 1.5'. The structure type 2' is realized for [(Ph-C C) 2 Mg(dx) 2 ] 1 (2'-C 2 Ph), [MgCl 2 (dx) 2 ] 1 (2'-Cl), and [MgBr 2 (dx) 2 ] 1 (2'-Br) with hexacoordinate metal atoms. The solubility of the dioxane adducts in common organic solvents strongly depends on the degree of aggregation with the solubility decreasing from molecular to strand to layer structures.[a] Dr.Scheme 2. Dioxane method to shift the Schlenk equilibrium of organylmagnesium halides toward soluble [R 2 Mg(dx) n ] and insoluble [MgX 2 (dx) 2 ] 1 by substitution of the Lewis base L (e.g., diethyl ether or thf) by 1,4-dioxane (dx).Scheme 3. Structural diversity of hitherto known 1,4-dioxane adducts of diorganylmagnesium complexes authenticated by X-ray crystal-structure determinations.

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(Dioxane)dineopentylmagnesium: a polymeric structure

Cited by 11 publications

References 7 publications

1,4-Dioxane Adducts of Grignard Reagents: Synthesis, Ether Fragmentation Reactions, and Structural Diversity of Grignard Reagent/1,4-Dioxane Complexes

1,4-Dioxane Adducts of Grignard Reagents: Synthesis, Ether Fragmentation Reactions, and Structural Diversity of Grignard Reagent/1,4-Dioxane Complexes

N-Heterocyclic carbene stabilized adducts of alkyl magnesium amide, bisalkyl magnesium and Grignard reagents: trapping oligomeric organo s-block fragments with NHCs

Structure–Solubility Relationship of 1,4‐Dioxane Complexes of Di(hydrocarbyl)magnesium

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