Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium

Timo Bollermann; Thomas Cadenbach; Christian Gemel; Kerstin Freitag; Mariusz Molon; Vanessa Gwildies; Roland A. Fischer

doi:10.1021/ic200699f

Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium

Timo Bollermann, Thomas Cadenbach, Christian Gemel, Kerstin Freitag, Mariusz Molon, Vanessa Gwildies, Roland A. Fischer

Ruhr-Universität Bochum

Producción científica: Contribución a una revista › Artículo › revisión exhaustiva

23 Citas (Scopus)

Resumen

The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC₆H ₃-2,6-ⁱPr₂)₂) were investigated and compared. Treatment of [Mo(η⁴-butadiene)₃] with GaCp* under hydrogen atmosphere at 100 °C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)₆] (1) in good yields ≥50%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa₆] core. Similarly, [Rh(GaCp*) ₅][CF₃SO₃] (2) and [Rh(GaCp*) ₅][BAr^F] (3) (BAr^F = B{C₆H ₃(CF₃)₂}₄) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe) ₂(CF₃SO₃)]₂ (coe = cyclooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa₅] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)₂(CF₃SO₃)]₂ does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF₃SO₃)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF ₃SO₂O•••Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature ¹H and ¹³C NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.

Idioma original	Inglés
Páginas (desde-hasta)	5808-5814
Número de páginas	7
Publicación	Inorganic Chemistry
Volumen	50
N.º	12
DOI	https://doi.org/10.1021/ic200699f
Estado	Publicada - 20 jun. 2011
Publicado de forma externa	Sí

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@article{a957d1d1ddd24143b4b028c36ea10a6e,

title = "Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium",

abstract = "The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC6H 3-2,6-iPr2)2) were investigated and compared. Treatment of [Mo(η4-butadiene)3] with GaCp* under hydrogen atmosphere at 100 °C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)6] (1) in good yields ≥50%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa6] core. Similarly, [Rh(GaCp*) 5][CF3SO3] (2) and [Rh(GaCp*) 5][BArF] (3) (BArF = B{C6H 3(CF3)2}4) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe) 2(CF3SO3)]2 (coe = cyclooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa5] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)2(CF3SO3)]2 does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF3SO3)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF 3SO2O•••Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature 1H and 13C NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.",

author = "Timo Bollermann and Thomas Cadenbach and Christian Gemel and Kerstin Freitag and Mariusz Molon and Vanessa Gwildies and Fischer, {Roland A.}",

year = "2011",

month = jun,

day = "20",

doi = "10.1021/ic200699f",

language = "Ingl{\'e}s",

volume = "50",

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journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium

AU - Bollermann, Timo

AU - Cadenbach, Thomas

AU - Gemel, Christian

AU - Freitag, Kerstin

AU - Molon, Mariusz

AU - Gwildies, Vanessa

AU - Fischer, Roland A.

PY - 2011/6/20

Y1 - 2011/6/20

N2 - The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC6H 3-2,6-iPr2)2) were investigated and compared. Treatment of [Mo(η4-butadiene)3] with GaCp* under hydrogen atmosphere at 100 °C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)6] (1) in good yields ≥50%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa6] core. Similarly, [Rh(GaCp*) 5][CF3SO3] (2) and [Rh(GaCp*) 5][BArF] (3) (BArF = B{C6H 3(CF3)2}4) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe) 2(CF3SO3)]2 (coe = cyclooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa5] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)2(CF3SO3)]2 does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF3SO3)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF 3SO2O•••Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature 1H and 13C NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.

AB - The reactions of molybdenum(0) and rhodium(I) olefin containing starting materials with the carbenoid group 13 metal ligator ligand GaR (R = Cp*, DDP; Cp* = pentamethylcyclopentadienyl, DDP = HC(CMeNC6H 3-2,6-iPr2)2) were investigated and compared. Treatment of [Mo(η4-butadiene)3] with GaCp* under hydrogen atmosphere at 100 °C yields the homoleptic, hexa coordinated, and sterically crowded complex [Mo(GaCp*)6] (1) in good yields ≥50%. Compound 1 exhibits an unusual and high coordinated octahedral [MoGa6] core. Similarly, [Rh(GaCp*) 5][CF3SO3] (2) and [Rh(GaCp*) 5][BArF] (3) (BArF = B{C6H 3(CF3)2}4) are prepared by the reaction of GaCp* with the rhodium(I) compound [Rh(coe) 2(CF3SO3)]2 (coe = cyclooctene) and subsequent anion exchange in case of 3. Compound 2 features a trigonal bipyramidal [RhGa5] unit. In contrast, reaction of excess Ga(DDP) with [Rh(coe)2(CF3SO3)]2 does not result in a high coordinated homoleptic complex but instead yields [(coe)(toluene)Rh{Ga(DDP)}(CF3SO3)] (4). The common feature of 2 and 4 in the solid state structure is the presence of short CF 3SO2O•••Ga contacts involving the GaCp* or rather the Ga(DDP) ligand. Compounds 1, 2, and 4 have been fully characterized by single crystal X-ray diffraction, variable temperature 1H and 13C NMR spectroscopy, IR spectroscopy, mass spectrometry, as well as elemental analysis.

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U2 - 10.1021/ic200699f

DO - 10.1021/ic200699f

M3 - Artículo

AN - SCOPUS:79958790282

SN - 0020-1669

VL - 50

SP - 5808

EP - 5814

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 12

ER -

Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium

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