Sterically Demanding Fluorinated Substituents and Metal Fluorides with Bulky Ligands

Witt, Michael; Roesky, Herbert W.

doi:10.1002/9780470166413.ch5

Cited by 24 publications

(2 citation statements)

References 289 publications

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“…Fluorinated arene ligands are likely to engage in π–π interactions because of the polar nature of the C–F bond. These fluorinated rings impart useful characteristics, including superior solubility/volatility properties and the stabilization of elements in high oxidation states.…”

Section: Introductionmentioning

confidence: 99%

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

et al. 2015

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Reductive cleavage of C6F5SeSeC6F5 with elemental M (M = Cu, In, Sn, Pb) in pyridine results in the formation of (py)4Cu2(SeC6F5)2, (py)2In(SeC6F5)3, (py)2Sn(SeC6F5)2, and (py)2Pb(SeC6F5)2. Each group adopts a unique structure: the Cu(I) compound crystallizes as a dimer with a pair of bridging selenolates, two pyridine ligands coordinating to each Cu(I) ion, and a short Cu(I)-Cu(I) distance (2.595 Å). The indium compound crystallizes as monometallic five-coordinate (py)2In(SeC6F5)3 in a geometry that approximates a trigonal bipyramidal structure with two axial pyridine ligands and three selenolates. The tin and lead derivatives (py)2M(SeC6F5)2 are also monomeric, but they adopt nearly octahedral geometries with trans pyridine ligands, a pair of cis-selenolates, and two "empty" cis-positions on the octahedron that are oriented toward extremely remote selenolates (M-Se = 3.79 Å (Sn), 3.70 Å (Pb)) from adjacent molecules. Two of the four compounds (Cu, In) exhibit intermolecular π-π stacking arrangements in the solid state, whereas the stacking of molecules for the other two compounds (Sn, Pb) appears to be based upon molecular shape and crystal packing forces. All compounds are volatile and decompose at elevated temperatures to give MSex and Se(C6F5)2.The electronic structures of the dimeric Cu compound and monomeric (py)2M(SeC6F5)2 (M = Sn, Pb) were examined with density functional theory calculations.

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Section: Introductionmentioning

confidence: 99%

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

et al. 2015

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“…With 50% probability thermal ellipsoids. Selected interatomic bond distances [] and angles[8] of 6: N(2)ÀN(3), 1.278(4); N(1)ÀN(2), 1.313(6); N(3)ÀC(5), 1.424(4); and N(1)ÀN(2)ÀN(3), 113.22(12); N(2)ÀN(3)ÀC(5) 111.55(12), respectively.…”

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confidence: 99%

Synthesis and Characterization of m‐Terphenyl (1,3‐Diphenylbenzene) Compounds Containing Trifluoromethyl Groups

Corona-Armenta

Ordóñez

López

et al. 2015

Helvetica Chimica Acta

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This work is dedicated to Prof. Ernesto Carmona a mentor, friend, and colleague.The bis(silyl)triazene compound 2,6-(Me 3 Si) 2 -4-Me-1-(N¼NÀNC 4 H 8 )C 6 H 2 (4) was synthesized by double lithiation/silylation of 2,6-Br 2 -4-Me-1-(N¼NÀNC 4 H 8 )C 6 H 2 (1). Furthermore, 2,6-bis[3,5-(CF 3 ) 2 -C 6 H 3 ]-4-Me-C 6 H 2 -1-(N¼NÀNC 4 H 8 )C 6 H 2 derivative 6 can be easily synthesized by a C,C-bond formation reaction of 1 with the corresponding aryl-Grignard reagent, i.e., 3,5-bis[(trifluoromethyl)phenyl]magnesium bromide. Reactions of compound 4 with KI and 6 with I 2 afforded in good yields novel phenyl derivatives, 2,6-(Me 3 Si) 2 -4-MeC 6 H 2 ÀI and 2,6-bis[3,5-(CF 3 ) 2 ÀC 6 H 3 ]-4-MeC 6 H 2 ÀI (5 and 7, resp.). On the other hand, the analogous m-terphenyl 1,3-diphenylbenzene compound 2,6-bis[3,5-(CF 3 ) 2 ÀC 6 H 3 ]C 6 H 3 ÀI (8) could be obtained in moderate yield from the reaction of (2,6-dichlorophenyl)lithium and 2 equiv. of aryl-Grignard reagent, followed by the reaction with I 2 . Different attempts to introduce the t Bu (Me 3 C) or neophyl (PhC(Me) 2 CH 2 ) substituents in the central ring were unsuccessful. All the compounds were fully characterized by elemental analysis, melting point, IR and NMR spectroscopy. The structure of compound 6 was corroborated by single-crystal X-ray diffraction measurements.

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Metallorganische Titankomplexe mit ungepaarten Elektronen: Synthese und Struktur von [{(η⁵‐Cp)₂TiF₂}₃Ti und [{(η⁵‐Cp')₂TiF₂}₃Al]

Liu¹,

Stallze²,

Roesky³

1993

Angewandte Chemie

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Sterically Demanding Fluorinated Substituents and Metal Fluorides with Bulky Ligands

Cited by 24 publications

References 289 publications

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

Synthesis and Characterization of m‐Terphenyl (1,3‐Diphenylbenzene) Compounds Containing Trifluoromethyl Groups

Metallorganische Titankomplexe mit ungepaarten Elektronen: Synthese und Struktur von [{(η⁵‐Cp)₂TiF₂}₃Ti und [{(η⁵‐Cp')₂TiF₂}₃Al]

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Sterically Demanding Fluorinated Substituents and Metal Fluorides with Bulky Ligands

Cited by 24 publications

References 289 publications

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSex

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSex

Synthesis and Characterization of m‐Terphenyl (1,3‐Diphenylbenzene) Compounds Containing Trifluoromethyl Groups

Metallorganische Titankomplexe mit ungepaarten Elektronen: Synthese und Struktur von [{(η5‐Cp)2TiF2}3Ti und [{(η5‐Cp')2TiF2}3Al]

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Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe_x

Metallorganische Titankomplexe mit ungepaarten Elektronen: Synthese und Struktur von [{(η⁵‐Cp)₂TiF₂}₃Ti und [{(η⁵‐Cp')₂TiF₂}₃Al]