Silver tetrakis(hexafluoroisopropoxy)aluminate as hexafluoroisopropyl transfer reagent for the chlorine/hexafluoroisopropyl exchange in imino phosphanes

Kuprat, Marcus; Kuzora, René; Lehmann, Mathias; Schulz, Axel; Villinger, Alexander; Wustrack, Ronald

doi:10.1016/j.jorganchem.2009.11.014

Cited by 16 publications

(13 citation statements)

References 28 publications

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“…[17] 4 ] (5) is easily generated in good yields (51 %) by utilizing 4-cyano-2,3,5,6-tetrafluorophenol, HO-C 6 F 4 -CN, as shown in Scheme 4, in the reaction of NaBH 4 with HO-C 6 F 4 -CN in acetonitrile only the formation of Na(O-C 6 F 4 -CN) (6), the free acid B(O-C 6 F 4 -CN) 3 , and molecular hydrogen (Scheme 5) is observed. A similar Lewis acid/Lewis base reaction is assumed to occur for weakly coordinating anions of the type [Al(OR F ) 4 ]or [B(C 6 F 5 ) 4 ]in the presence of very electrophilic cations, in which the decomposition is initiated either by ligand (R F O -, [18,19] C 6 F 5 -) [20] or fluoride ion abstraction. Obviously, the driving force for the formation of 6 is the instability of the [B(O-C 6 F 4 -CN) 4 ]anion towards strong electrophilic ions.…”

Section: Resultsmentioning

confidence: 99%

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Molecular Networks Based on CN Coordination Bonds

et al. 2012

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This study examines the use of tetrahedral [E(O–C6X4–CN)4]– anions (E = B, Al; X = H, F), which can be synthesized from the reaction of tetrahedral NaBH4/LiAlH4 and HO–C6X4–CN, as anionic linkers for the generation of 2D and 3D crystalline coordination polymer networks. Such polymer networks were obtained by the connection of tetrahedral p‐cyanophenoxy aluminate or borate linkers with monocationic metal centers such as Li+, Na+, Ag+, and Cu+. These studies are specifically focused on the synthesis, structure, and stability of such polymers. Additionally, the perfluorinated O–C6F4–CN linker was used to study electronic influences. Salts bearing the perfluorinated [E(O–C6F4–CN)4]– anion decompose into E(O–C6F4–CN)3 and [O–C6F4–CN]–, which is also observed when a Lewis acid such as B(C6F5)3 is added. Moreover, addition of B(C6F5)3 leads to the formation of molecular‐ion pairs because the cyano groups are now either completely or partly blocked. The structures of M[Al(O–C6H4–CN)4] (M = Li, Ag, Cu), Na[B(O–C6H4–CN)4], and Li[Al(O–C6F4–CN)4] as well as of the decomposition products Na(O–C6F4–CN), (THF)Al[O–C6H4–CN·B(C6F5)3]3 (THF = tetrahydrofuran), Na[(F5C6)3B·O–C6H4–CN·B(C6F5)3], and Li[NC–C6F4–O–Al{O–C6F4–CN·B(C6F5)3}3] are discussed.

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Section: Resultsmentioning

confidence: 99%

“…They slowly decompose in water with the formation of the free alcohol HO-C 6 X 4 -CN and B 2 O 3 ·nH 2 O and Al 2 O 3 ·nH 2 O as shown by 1 H, 19 F, and 11 B NMR studies. They dissolve in solvents such as CH 3 CN or THF but not in CH 2 Cl 2 or benzene.…”

Section: Propertiesmentioning

confidence: 99%

Molecular Networks Based on CN Coordination Bonds

et al. 2012

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“…[1] In particular, we have always had great interest in NE chemistry, for example, the synthesis of cyclo-dipnictadiazanes [XE(m-NR)] 2 (A, X= (pseudo)halogen). [2][3][4][5][6][7][8][9][10] These four-membered ring systems are closely related to the highly reactive haloiminopnictanes RN=EX (B), since they can be regarded as formal dimers of the latter (Scheme 1). The stability of the monomeric iminopnictanes in comparison with the corresponding dimeric cyclo-dipnictadiazanes depends on the size of the sterically demanding substituent R. [11,12] For example, the supermesityl substituent (Mes* = 2,4,6-tri-tert-butylphenyl) favours the formation of the monomeric iminophosphane Mes*NPCl (1), which is stable in the solid state and in solution.…”

Section: Introductionmentioning

confidence: 99%

“…[18] Upon treatment with iodine, the similar tetraphosphenediide Tl 2 [Ter'PPPPTer'] (4 b, Ter' = 2,6-(2,6-diisopropylphenyl)phenyl) gave the bicyclotetraphosphane Ter'P 4 Ter' (5 a), which can be regarded as the formal reduction product of [XP(m-PTer')] 2 . [19] Concerning halogen-substituted diphosphenes, the formal monomers of the discussed cyclo-tetraphosphanes, the only reported example is Mes*PPCl (6), which was proposed to be the labile intermediate of the reaction of Mes*PPN(iPr) 2 (7) with various organolithium compounds (RLi) in the presence of HCl, leading to differently substituted diphosphenes of the type Mes*PPR. [20] However, no analytical information proving the formation of 6 was given in the publication, and thus its existence is uncertain.…”

Section: Introductionmentioning

confidence: 99%

Dimers and Trimers of Diphosphenes: A Wealth of Cyclo‐Phosphanes

Bresien

Hering

Schulz

et al. 2014

Chemistry A European J

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Various new P-based ring systems were synthesised by transferring established reaction routes from NP chemistry to the analogous PP compounds. Due to the different electronic situations of phosphorus and nitrogen with respect to s and p character of the lone pair, different reactivity of the phosphorus compounds was observed, especially with regard to the specificity of the reactions and the stability of the products. Whereas Mes*NPCl (Mes*=2,4,6-tri-tert-butylphenyl) is stable in the solid state and in solution, the formal phosphorus congener Mes*PPCl is highly reactive and could not be observed. Instead, several formal dimers and trimers of Mes*PPCl could be isolated, which constitute an intriguing variety of three- and four-membered ring systems.

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“…To combine a decent stability with sufficient Lewis acidity, we chose the fluorinated alkoxide 1,1,1,3,3,3-hexafluoro-2-propoxy ligand (Ohfip) for the boryl residue. The Ohfip-ligand was proven to provide suitable Lewis acidity to an electron-deficient central atom, e.g., in the related B(Ohfip) 3 , as well as in monomeric Al[OC(CF 3 ) 3 ] 3 or dimeric Al 2 (Ohfip) 6 [30][31][32][33][34]. Carpenter and coworkers suggested that oxidation enhances the Lewis acidity of ferrocenylboranes, so that the B center in certain borylferrocinium compounds abstracts a fluoride from a [BF 4 ] -counteranion [35].…”

Section: Introductionmentioning

confidence: 99%