Terphenyl Ligands and Complexes

Lummis, Paul A.; Wang, Shuai; Gavenonis, John; Schüwer, Nicolas; Tilley, T. Don; Boynton, Jessica N.; Weidemann, Nils; Ditri, Treffly B.; Barnett, Brandon R.; Mokhtarzadeh, Charles C.; Smith, Patrick W.; Pratt, Jade; Mendelson, Noah D.; Queen, Joshua D.; Power, Philip P.; Agnew, Douglas W.; Carpenter, Alex E.; Figueroa, Joshua S.

doi:10.1002/9781119477822.ch5

Cited by 13 publications

(14 citation statements)

References 91 publications

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“…The solid terphenyl thiol HSAr iPr4 (0.43 g, 1 mmol) was mixed with solid mesitylcopper(I) (0.182 g, 1 mmol), and ca. 60 mL of THF was added.…”

Section: Methodsmentioning

confidence: 99%

“…The synthesis of 2 was accomplished in a similar manner to the preparation of 1 with the use of the terphenyl thiol HSAr iPr6 (0.514 g, 1 mmol) and mesitylcopper(I) (0.182 g, 1 mmol) in ca. 60 mL of THF, which yielded 0.155 g (27%) of colorless crystals which were suitable for X-ray crystallography.…”

Section: Methodsmentioning

confidence: 99%

“…n -BuLi (0.31 mL of a 2.5 M solution in n -hexane) was added dropwise to a stirred solution of HSAr iPr4 (0.30 g, 0.7 mmol) in ca. 30 mL of toluene at 0 °C.…”

Section: Methodsmentioning

confidence: 99%

“…UV−vis spectra were recorded as dilute hexane solutions in 3.5 mL quartz cuvettes using an Olis 17 modernized Cary 14 UV−vis−near-IR spectrophotometer or an HP 8452 diode-array spectrophotometer. The terphenyl thiols HSAr iPr4 , HSAr iPr6 , 45 and mesitylcopper(I) 46 were prepared via literature methods. Unless otherwise stated, all materials were obtained from commercial sources and used as received.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

et al. 2021

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The direct reactions of the large terphenyl thiols HSAr iPr4 (Ar iPr4 = −C 6 H 3 -2,6-(C 6 H 3 -2,6-iPr 2 ) 2 ) and HSAr iPr6 (Ar iPr6 = −C 6 H 3 -2,6-(C 6 H 2 -2,4,6-iPr 3 ) 2 ) with stoichiometric amounts of mesitylcopper(I) in THF at ca. 80 °C afforded the first well-characterized dimeric copper thiolato species {CuSAr iPr4 } 2 (1) and {CuSAr iPr6 } 2 (2) with elimination of mesitylene. The complexes 1 and 2 were characterized by NMR and electronic spectroscopy as well as by X-ray crystallography. They have dimeric Cu 2 S 2 core structures in which the two copper atoms are bridged by the sulfurs from the thiolato ligands and feature short Cu--Cu distances near 2.4 Å as well as a weak copper-flanking aryl ring interaction from a terphenyl substituent. The structures of the planar Cu 2 S 2 cores bear a resemblance to the Cu A site in nitrous oxide reductase in which two cysteines also bridge two copper atoms. The related dimeric Li 2 S 2 structural motif was also observed in the lithium congeners {LiSAr iPr4 } 2 (3) and {LiSAr iPr6 } 2 (4) which were synthesized directly from the thiols and n-BuLi in hexanes. However, despite the very similar effective ionic radii of the Li + (0.59 Å) and Cu + (0.60 Å) ions, the Li--Li structures display very much longer (by more than ca. 0.5 Å) separations than the corresponding Cu--Cu distances in 1 and 2, which may be due to weaker dispersion interactions.

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“…The solid terphenyl thiol HSAr iPr4 (0.43 g, 1 mmol) was mixed with solid mesitylcopper(I) (0.182 g, 1 mmol), and ca. 60 mL of THF was added.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…n -BuLi (0.31 mL of a 2.5 M solution in n -hexane) was added dropwise to a stirred solution of HSAr iPr4 (0.30 g, 0.7 mmol) in ca. 30 mL of toluene at 0 °C.…”

Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

et al. 2021

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“…Nonetheless, the increased reactivity of acid chlorides can enable the construction of more crowded, decorated β-diketones, albeit in poor yields and with difficult separations. , Acid chlorides derived from m -terphenyls show a remarkably slowed reactivity . This very encumbering moiety has stabilized extremely reactive, low-coordinate metal complexes. − We have previously shown that a m -terphenyl appended to a β-diketone enables steric control of a metal’s coordination sphere, a historically difficult challenge for acac-type ligands. − Here, we describe the preparation and synthetic considerations of a range of sterically hindered β-diketones.…”

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confidence: 99%

Synthesis of Sterically Hindered β-Diketones via Condensation of Acid Chlorides with Enolates

et al. 2019

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Bulky β-diketones have rarely exceeded dipivaloylmethane (DPM) in steric demand, largely due to synthetic limitations of the Claisen condensation. This work demonstrates hindered acid chlorides to be selective electrophiles in noncoordinating solvents for condensations with enolates. An improved synthesis of DPM is described (90% yield), and crowded β-diketones featuring bulky o-biphenyl or m-terphenyl fragments were prepared in good to excellent yields. These compounds are anticipated to have a steric profile far greater than that of DPM. General reaction conditions and mechanistic considerations are included.

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A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

English

Pajak

McMullin

et al. 2022

Chemistry A European J

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Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand Ar iPr4 (Ar iPr4 = [C 6 H 3 -2,6-(C 6 H 3 -2,6-iPr 2 )]) at 150 °C gives [Ar iPr4 PO 2 ] 2 via loss of ethene.[Ar iPr4 PO 2 ] 2 was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered PÀ OÀ PÀ O ring and is the isostructural oxygen analogue of Lawesson's and Woollins' reagents. The dimeric structure of [Ar iPr4 PO 2 ] 2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give Ar iPr4 (DMAP)PO 2 after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [Ar iPr4 PO 2 ] 2 in 75 % yield in 2 days at only 100 °C.

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Terphenyl Ligands and Complexes

Cited by 13 publications

References 91 publications

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Synthesis of Sterically Hindered β-Diketones via Condensation of Acid Chlorides with Enolates

A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

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