Reactions of alkali metal and yttrium alkyls with a sterically demanding bis(aryloxysilyl)methane: Formation of aryloxide complexes by Si-O bond cleavage

Cornish, Andrew D.; Mills, David P.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

doi:10.1016/j.crci.2010.01.017

Cited by 10 publications

(1 citation statement)

References 59 publications

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“…For further comparison, the terminal Y–C(CH 3 ) distances ( 5-Y : 2.409(2) Å, 6-Y : 2.404(2) Å) are similar to those detected for Tp t Bu,Me YMe(AlMe 4 ) (2.382(3) Å) and Y(CH 3 )[(AlMe 2 ){OSi(O t Bu) 3 } 2 ][OSi(O t Bu) 3 ] (2.438(2) Å) . Similarly, the Ln–O distances in complexes 5-Ln and 6-Ln lie in the expected range, e.g., Y(OC 6 H 2 Me 3 -2,4,6) 3 (THF) 3 (Y–O: 2.104(4)–2.114(5) Å), [Y(μ-OC 6 H 3 Me 2 -2,6)(OC 6 H 3 Me 2 -2,6) 2 (THF)] 2 (Y–O terminal : 2.046 (6) Å, 2.075(6) Å), 1-Lu (2.052(2), 2.06(2) Å), Ln(OC 6 H 3 i Pr 2 -2,6) 3 (THF) 2 (Y: 2.065(7)–2.086(7) Å and 2.069(3)–2.086(2) Å; Lu: av. 2.044 Å) .…”

Section: Resultssupporting

confidence: 69%

Mixed Methyl Aryloxy Rare-Earth-Metal Complexes Stabilized by a Superbulky Tris(pyrazolyl)borato Ligand

2019

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Various mixed methyl aryloxide complexes Tp tBu,Me LnMe(OAr) (Ln = Y, Lu) were obtained in moderate to high yields according to distinct synthesis protocols dependent on the metal size and sterics of the phenolic proligand. The reaction of Tp tBu,Me LuMe 2 and Tp tBu,Me YMe(AlMe 4 ) via protonolysis with 1 or 2 equiv HOC 6 H 2 tBu 2 -2,6-Me-4 in n-hexane gave the desired complexes Tp tBu,Me LnMe(OAr). Corresponding treatment of Tp tBu,Me LuMe 2 with the sterically less demanding HOC 6 H 3 Me 2 -2,6, HOC 6 H 3 iPr 2 -2,6 and HOC 6 H 3 (CF 3 ) 2 -3,5 led to the formation of the bis(aryloxy) lutetium complexes Tp tBu,Me Lu(OAr) 2 . Application of a salt-metathesis protocol employing Tp tBu,Me LnMe(AlMe 4 ) and the potassium aryloxides KOAr made complexes Tp tBu,Me LnMe(OAr) accessible for the smaller aryloxy ligands as well. All complexes were analyzed by X-ray crystallography to compare the terminal Ln−Me bond lengths and to evaluate the implication of the methyl/aryloxy coordination for the exact cone angles Θ°of the [Tp tBu,Me ] ancillary ligand. Treatment of Tp tBu,Me LnMe(AlMe 4 ) (Ln = Lu, Y) with HOC 6 H 2 tBu 2 -2,6-Me-4 in the presence of 4-(dimethylamino)pyridine (dmap) produced ion-separated complexes [Tp tBu,Me LnMe(dmap) 2 ]-[Me 3 AlOC 6 H 2 tBu 2 -2,6-Me-4)]. The thermal instability of Tp tBu,Me LuMe(OC 6 H 2 tBu 2 -2,6-Me-4) was revealed by the formation of (Tp (tBu-H)/(tBu)2,Me )Lu(OC 6 H 2 tBu 2 -2,6-Me-4) via intramolecular C−H-bond activation.

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Section: Resultssupporting

confidence: 69%

Mixed Methyl Aryloxy Rare-Earth-Metal Complexes Stabilized by a Superbulky Tris(pyrazolyl)borato Ligand

2019

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Ligand Design in Modern Lanthanide Chemistry

Mills

Liddle

2016

Ligand Design in Metal Chemistry

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Supramolecular Chemistry Based on Frustrated Lewis Pairs – Reactions of an Al/P FLP with Potassium Formate and Cesium Fluoride

Uhl

Lange

Hepp

et al. 2018

Zeitschrift anorg allge chemie

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Reactions of the Al/P‐based frustrated Lewis pair Mes2P–C(AltBu2)=C(H)–Ph (1) with the Brønstedt acids HBr, HI, and HCO2H resulted in the formation of the corresponding HX adducts Mes2(H)P–C[Al(X)tBu2]=C(H)–Ph [X = Br (4), I (5), OC(H)O (6)]. Despite the well‐known sensitivity of Al–C bonds towards protolysis, the products were isolated in good yields. Short intramolecular distances between H and Br, I or O are consistent with the presence of P–H···X hydrogen bonds. Treatment of 1 with potassium formate or CsF yielded in poor to moderate yields the adducts Mes2P–C(AltBu2)=C(H)Ph·(KO2CH) (7) and Mes2P–C(AltBu2)=C(H)Ph·(CsF) (8). The potassium compounds required the presence of additional solvent molecules to obtain isolable crystalline products. Two monomeric units were joined by interactions of each K+ cation with two formate anions. Supramolecular entities resulted by the additional coordination of the K+ cations to solvent molecules (7a, toluene; 7b, 1,2‐difluorobenzene; 7c, THF), weak contacts to a mesityl group and in case of 7b and 7c to a tBu group and the P atom. The CsF adduct 8 crystallizes as a double‐stranded chain with the coordination of the Cs+ cation to F–, a mesityl group (η6), a Ph group (η6; leads to an infinite chain), and a tBu group (connects two chains to a double strand) of two different neighboring molecules. The Cs–F bond length is with 274.7(1) pm comparatively short, and the adduct may be viewed as a CsF molecule trapped by the FLP functionality.

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Reactions of alkali metal and yttrium alkyls with a sterically demanding bis(aryloxysilyl)methane: Formation of aryloxide complexes by Si-O bond cleavage

Cited by 10 publications

References 59 publications

Mixed Methyl Aryloxy Rare-Earth-Metal Complexes Stabilized by a Superbulky Tris(pyrazolyl)borato Ligand

Mixed Methyl Aryloxy Rare-Earth-Metal Complexes Stabilized by a Superbulky Tris(pyrazolyl)borato Ligand

Ligand Design in Modern Lanthanide Chemistry

Supramolecular Chemistry Based on Frustrated Lewis Pairs – Reactions of an Al/P FLP with Potassium Formate and Cesium Fluoride

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