Lanthanide-Group 12 Metal Chalcogenolates: A Versatile Class of Compounds

Berardini, M.; Emge, Thomas J.; Brennan, John G.

doi:10.1021/ic00125a036

Cited by 66 publications

(54 citation statements)

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“…Calcd for C33H30N3HoS3 : C,54.0;H,4.12;N,5.72. Found: C,50.1;H,3.86;N,5.47 (2)°, V ) 7021(4) Å 3 . Thermolysis: 1 (650 mg) was placed in a Pyrex tube under vacuum for 1 h. The tube was then sealed, and the sample temperature was raised over a period of 3 days from 50 to 300°C, with one end of the tube kept at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…Calcd for C22H23OS3Sm: C,48.05;H,4.21. Found: C,43.40;H,4.13. The compound does not show a λmax from 350 to 800 nm in THF.…”

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

“…Anal. Calcd for C33H30N3Se3Sm : C,46.3;H,3.53;N,4.90. Found: C,43.28;H,3.59;N,4.48 Synthesis of [(THF)4Nd3(SePh)9]n (10).…”

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

“…Calcd for C33H30N3Se3Sm : C,46.3;H,3.53;N,4.90. Found: C,43.28;H,3.59;N,4.48 Synthesis of [(THF)4Nd3(SePh)9]n (10). Nd (0.58 g, 4.0 mmol), Ph2Se2 (1.89 g, 6.0 mmol), and Hg (50 mg, 0.25 mmol) were stirred in THF (50 mL) for 2 days.…”

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

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Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

et al. 1998

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A series of trivalent lanthanide (Ln) benzenechalcogenolate (EPh, E ) S, Se) complexes have been prepared and structurally characterized in an attempt to evaluate how metal size, chalcogen, and solvent influence structure and physical properties. The compounds [(py) 3 Ln(SPh) 3 ] 2 (Ln ) Ho (1) and Tm (2)), [(py) 2 Sm(SPh) 3 ] 4 (3), [(THF)Sm(SPh) 3 ] 4n (4), (THF) 3 Ln(SePh) 3 (Ln ) Tm (5), Ho (6), Er (7)), [(py) 3 Sm(SePh) 3 ] 2 (8), and [(THF) 4 Ln 3 -(SePh) 9 ] n (Ln ) Pr (9), Nd (10), and Sm (11)) were isolated and characterized by IR, NMR, and UV-visible spectroscopy. Compounds 2-4, 7, 8, and 10 have also been characterized by low-temperature single-crystal X-ray diffraction. Three trends in structure are clear. First, the tendency to form oligomeric structures is found to increase with the size of the lanthanide ion. Second, thiolates bridge metal ions to form polynuclear structures more effectively than selenolates. Finally, pyridine displaces bridging chalcogenolates to form less extended structures more effectively than THF. Compounds 5-7 are molecular fac-octahedral complexes, compounds 1, 2, and 8 are bimetallic molecules with a pair of chalcogen atoms spanning the pentagonal bipyramidal metal centers, compound 3 is a tetrametallic structure with an alternating (3-2-3) number of µ 2 -thiolates spanning the linear assembly of four seven-coordinate Sm(III) ions, and compounds 4, 9, 10, and 11 are polymers with sets of three doubly bridging benzenechalcogenolates connecting adjacent metal ions. Resonance Raman spectroscopy indicates that the intense electronic absorption associated with Sm(III) chalcogenolate is a chalcogen-to-metal charge-transfer excitation. Compounds 1 and 2 decompose thermally to give Ln 2 S 3 .

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Section: Methodsmentioning

confidence: 99%

“…Calcd for C22H23OS3Sm: C,48.05;H,4.21. Found: C,43.40;H,4.13. The compound does not show a λmax from 350 to 800 nm in THF.…”

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

“…Anal. Calcd for C33H30N3Se3Sm : C,46.3;H,3.53;N,4.90. Found: C,43.28;H,3.59;N,4.48 Synthesis of [(THF)4Nd3(SePh)9]n (10).…”

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

Section: Synthesis Of [(Thf)sm(sph)3]4n (4)mentioning

confidence: 99%

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Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

et al. 1998

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“…The equimolar reaction did not yield the en- [20] The barium center in complex 5 adopts a square antiprismatic coordination geometry.…”

Section: Resultsmentioning

confidence: 96%

Diene Dissolution of the Heavier Alkaline Earth Metals

et al. 2012

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Alkaline and alkaline earth metals are efficiently activated in the presence of aromatic hydrocarbons ("potassium-naphthalene", "magnesium-anthracene") or (substituted) 1,3-dienes to produce well-defined organometallic complexes. In this study, mononuclear diene complexes of calcium, strontium, and barium have been synthesized by utilizing tailormade 1,3-dienes. Complexes [M(2,3-dimethyl-1,4-ditolyl-1,3-butadiene)(thf) 4 ] (M = Ca, Sr), [Ca(2,3-dimethyl-1,4-dinaphthyl-1,3-butadiene)(thf) 4 ], and {Ba [2,3-dimethyl-1,4-

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Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

Lang

Dias

Abram

et al. 2000

Z. anorg. allg. Chem.

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The reaction of dibenzenediselenide, (SePh)2, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)2], in a good yield. (nBu4N)[Hg(SePh)3] is obtained by the reaction of [Hg(SePh)2] with a solution of [SePh]– and (nBu4N)Br in ethanol. The solid state structures of both compounds have been determined by X‐ray diffraction. The mercury atom in [Hg(SePh)2] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co‐ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)2] units to layers. The crystal structure of (nBu4N)[Hg(SePh)3] (space group P21/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (nBu4N)+ counter ions. The coordination geometry of mercury is distorted trigonal‐planar with Hg–Se distances ranging between 2.5 and 2.6 Å.

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Lanthanide-Group 12 Metal Chalcogenolates: A Versatile Class of Compounds

Cited by 66 publications

References 1 publication

Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

Diene Dissolution of the Heavier Alkaline Earth Metals

Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

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Lanthanide-Group 12 Metal Chalcogenolates: A Versatile Class of Compounds

Cited by 66 publications

References 1 publication

Trivalent Lanthanide Chalcogenolates: Ln(SePh)3, Ln2(EPh)6, Ln4(SPh)12, and [Ln(EPh)3]n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

Trivalent Lanthanide Chalcogenolates: Ln(SePh)3, Ln2(EPh)6, Ln4(SPh)12, and [Ln(EPh)3]n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

Diene Dissolution of the Heavier Alkaline Earth Metals

Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

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Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure

Trivalent Lanthanide Chalcogenolates: Ln(SePh)₃, Ln₂(EPh)₆, Ln₄(SPh)₁₂, and [Ln(EPh)₃]_n (E = S, Se). How Metal, Chalcogen, and Solvent Influence Structure