Potassium and Yttrium Complexes of a Rigid Bis‐Phosphido POP‐Donor Ligand

Motolko, Kelly S. A.; Emslie, David J. H.; Jenkins, Hilary A.; Britten, James F.

doi:10.1002/ejic.201700430

Cited by 7 publications

(3 citation statements)

References 60 publications

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“…1). These metric parameters are in line with those detected for 1a and 1c (Table S1†),31 of which the molecular structures have been reported previously 32,33…”

Section: Resultssupporting

confidence: 91%

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation

et al. 2019

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“…1). These metric parameters are in line with those detected for 1a and 1c (Table S1†),31 of which the molecular structures have been reported previously 32,33…”

Section: Resultssupporting

confidence: 91%

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation

et al. 2019

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“…Our group has previously employed rigid pincer ligands to prepare a range of organometallic and coordination complexes of electropositive actinide − and rare earth − elements. In addition, we recently reported the rigid thioether- and selenoether-containing ligands 4,5-bis(phenylsulfido)-2,7,9,9-tetramethylacridan (H[AS 2 Ph2 ] ( 1 )) and 4,5-bis(phenylselenido)-2,7,9,9-tetramethylacridan (H[ASe 2 Ph2 ] ( 2 )), their deprotonation to generate the potassium salts, and subsequent reactivity with [UI 4 (1,4-dioxane) 2 ] to afford [(AS 2 Ph2 ) 2 UI 2 ] and [(ASe 2 Ph2 ) 2 UI 2 ].…”

Section: Introductionmentioning

confidence: 99%

A Synthetic, Structural, Spectroscopic, and Computational Study of Alkali Metal–Thioether, −Selenoether, and −Telluroether Interactions

Gray,

Vargas-Baca,

Emslie

2023

Inorg. Chem.

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The rigid thioether-and selenoether-containing pro-ligands, 4,5-bis(phenylsulfido)-2,7,9,9-tetramethylacridan (H[AS 2 Ph2 ] (1)) and 4,5-bis(phenylselenido)-2,7,9,9-tetramethylacridan (H[ASe 2 Ph2 ] (2)), were deprotonated with one equiv of n BuLi to afford dimeric lithium complexes [Li(AE 2 Ph2 )] 2 (E = S (3), Se (4)) or with one equiv of KCH 2 Ph to afford the previously reported potassium complexes [K(AS 2 Ph2 )(dme)] x (5) and [K(ASe 2 Ph2 )(dme) 2 ] (6). Attempts to prepare a direct telluroether analogue of compounds 1−2 were unsuccessful. However, the bulky selenoether-and telluroether-containing pro-ligands 4,5bis(2,4,6-triisopropylphenylselenido)-2,7,9,9-tetramethylacridan (H[ASe 2 Tripp2 ] (7)) and 4,5-bis(2,4,6-triisopropylphenyltellurido)-2,7,9,9-tetramethylacridan (H[ATe 2 Tripp2] (8)) were accessed via the reaction of 4,5-dibromo-2,7,9,9-tetramethylacridan with three equiv of n BuLi, followed by the addition of two equiv of the corresponding diaryl dichalcogenide and quenching with dilute HCl (aq) . The new selenoether-and telluroether-containing pro-ligands were subsequently deprotonated using KCH 2 Ph to afford [K(AE 2 Tripp2 )(dme) 2 ] (E = Se (9), Te (10)). Compounds 1−10 were characterized by 1 H, 13 C{ 1 H}, 77 Se{ 1 H}, 125 Te{ 1 H}, and 7 Li NMR spectroscopy, where applicable, and single-crystal X-ray structures were obtained for all lithium and potassium complexes (3− 6 and 9−10). DFT calculations were also performed to assess the nature of bonding between the hard group 1 cations and the soft chalcogenoethers.

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“…Wagner and coworkers also reported the solid-state structure of a related alkyl-tethered bis(phosphido-borane) complex . A small number of transition metal complexes of alkyl-tethered α,ω-diphosphides have also been reported, − along with a selection of variously substituted aryl- or alkenyl-bridged diphosphide compounds. − …”

Section: Introductionmentioning

confidence: 99%

Influence of Chain Length on the Structures and Dynamic Behavior of Alkyl-Tethered α,ω-Diphosphide Complexes of Lithium and Their Use in the Synthesis ofP-Heterocyclic Stannylenes

et al. 2018

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The alkyl-tethered α,ω-diphosphines (Dipp)PH(CH2) n PH(Dipp) (n = 1 (3H), 2 (4H), 3 (5H), 4 (6H), and 5 (7H)) were prepared in good yield and characterized by multinuclear NMR spectroscopy [Dipp = 2,6-iPr2C6H3]. Treatment of 3H with 2 equiv of nBuLi and 2 equiv of TMEDA gives the diphosphide complex [CH2{P(Dipp)}2]Li2(TMEDA)2 (3Lia), which crystallizes as discrete monomers which do not exhibit temperature-dependent NMR behavior. Treatment of 4H–7H with 2 equiv of nBuLi in THF gives the diphosphides [[CH2{P(Dipp)}]2]2Li4(THF)2(OEt2)2 (4Li), [CH2{CH2P(Dipp)}2]Li2(THF)4 (5Li), [{CH2CH2P(Dipp)}2]Li2(THF)6 (6Li), and [CH2{CH2CH2P(Dipp)}2]2Li4(THF)6·PhMe (7Li) after crystallization. Compounds 4Li–7Li adopt either monomeric or dimeric structures in the solid state, depending on the length of the alkyl tether of the diphosphide ligand. In solution, compounds 4Li–7Li exhibit dynamic behavior: variable-temperature 31P{1H} and 7Li NMR spectroscopic studies indicate that this involves equilibria between monomeric and dimeric or higher oligomeric species with the nature of the equilibrium again depending on the length of the alkyl tether of the diphosphide ligand. The reactions between 3Li, 6Li, or 7Li and SnCl2 in THF give mixtures of products which could not be separated. In contrast, the reactions between 4Li or 5Li and 1 equiv of SnCl2 give the dimeric P-heterocyclic stannylenes [{CH2P(Dipp)}2Sn]2 (4Sn) and [CH2{CH2P(Dipp)}2Sn]2.1/2THF (5Sn), respectively. While compound 5Sn is isolated exclusively as the cis isomer, 4Sn is isolated as a mixture of cis and trans isomers in an approximate 5:1 ratio. The solid-state structures of trans-4Sn and cis-5Sn were obtained, and multinuclear NMR spectroscopy indicates that the dimeric structures of these compounds are maintained in solution. Compounds 4Sn and 5Sn represent the first P-heterocyclic stannylene dimers to be structurally characterized.

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Potassium and Yttrium Complexes of a Rigid Bis‐Phosphido POP‐Donor Ligand

Cited by 7 publications

References 60 publications

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation

A Synthetic, Structural, Spectroscopic, and Computational Study of Alkali Metal–Thioether, −Selenoether, and −Telluroether Interactions

Influence of Chain Length on the Structures and Dynamic Behavior of Alkyl-Tethered α,ω-Diphosphide Complexes of Lithium and Their Use in the Synthesis ofP-Heterocyclic Stannylenes

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