Synthesis and Structure of Alkoxy- and (Aryloxy)alanes. Observation of a Ring-Opening Reaction Involving Tetrahydrofuran

John P. Campbell, Wayne L Gladfelter

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34 Citations (Scopus)

Abstract

Dihydrogen elimination from aluminum hydrides and alcohols was used to produce new alkoxide and aryloxide complexes. Dimethylethylamine-alane (DMEAA) reacted with 2 equiv of 2,6-diisopropylphenol (DIPH) in THF at -78 °C to give (DIP)2:A1H·2THF (1) in 94% yield. It was characterized by NMR, IR, MS. and X-ray crystallography and found to be trigonal bipyramidal with both axial sites occupied by THF. Crystal data for 1: C32H51AlO4, monoclinic, C2/c, a = 21.37(1) Å, b = 9.324(3) Å, c = 15.30(1) Å, β = 94.16(5)°, V = 3040(5)Å3, Z = 4. DMEAA reacted with 2 equiv of triphenylcarbinol, Ph3COH, in THF at -78 °C to give (Ph3CO)2AIH· THF (2) in 42% yield. The lower coordination number was attributed to the larger cone angle of the ligand. Crystal data for 2: C42H39AlO3, triclinic, P1̄, a = 8.482(1) Å, b = 9.067(1) Å, c = 23.59(1)°, α = 90.919(1)°, β = 92.624(1)°, γ = 116.093(1)°, V = 1626.2(2) Å3, Z = 2. Three equivalents of DIPH in THF reacted with DMEAA at -78 °C to form the unexpected compound (DIP)3(THF)(NMe2Et)Al (3) in 89% yield. Both solution spectroscopic and X-ray crystallographic data established that THF underwent a ring-opening reaction. Crystal data for 3: C44H70AlNO4, monoclinic, Cc, a = 23.50(1) Å, b = 10.81(1) Å, c= 19.37(1) Å, β= 122.25(3)°, V = 4162(2) Å, Z = 4.

Original languageEnglish (US)
Pages (from-to)4094-4098
Number of pages5
JournalInorganic Chemistry
Volume36
Issue number18
StatePublished - Dec 1 1997

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tetrahydrofuran
Crystals
rings
synthesis
aluminum hydrides
crystals
X ray crystallography
alkoxides
Propofol
Aluminum
coordination number
Hydrides
crystallography
Cones
elimination
cones
alcohols
x rays
Alcohols
Nuclear magnetic resonance

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Synthesis and Structure of Alkoxy- and (Aryloxy)alanes. Observation of a Ring-Opening Reaction Involving Tetrahydrofuran. / Campbell, John P.; Gladfelter, Wayne L.

In: Inorganic Chemistry, Vol. 36, No. 18, 01.12.1997, p. 4094-4098.

Research output: Contribution to journalArticle

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title = "Synthesis and Structure of Alkoxy- and (Aryloxy)alanes. Observation of a Ring-Opening Reaction Involving Tetrahydrofuran",
abstract = "Dihydrogen elimination from aluminum hydrides and alcohols was used to produce new alkoxide and aryloxide complexes. Dimethylethylamine-alane (DMEAA) reacted with 2 equiv of 2,6-diisopropylphenol (DIPH) in THF at -78 °C to give (DIP)2:A1H·2THF (1) in 94{\%} yield. It was characterized by NMR, IR, MS. and X-ray crystallography and found to be trigonal bipyramidal with both axial sites occupied by THF. Crystal data for 1: C32H51AlO4, monoclinic, C2/c, a = 21.37(1) {\AA}, b = 9.324(3) {\AA}, c = 15.30(1) {\AA}, β = 94.16(5)°, V = 3040(5){\AA}3, Z = 4. DMEAA reacted with 2 equiv of triphenylcarbinol, Ph3COH, in THF at -78 °C to give (Ph3CO)2AIH· THF (2) in 42{\%} yield. The lower coordination number was attributed to the larger cone angle of the ligand. Crystal data for 2: C42H39AlO3, triclinic, P1̄, a = 8.482(1) {\AA}, b = 9.067(1) {\AA}, c = 23.59(1)°, α = 90.919(1)°, β = 92.624(1)°, γ = 116.093(1)°, V = 1626.2(2) {\AA}3, Z = 2. Three equivalents of DIPH in THF reacted with DMEAA at -78 °C to form the unexpected compound (DIP)3(THF)(NMe2Et)Al (3) in 89{\%} yield. Both solution spectroscopic and X-ray crystallographic data established that THF underwent a ring-opening reaction. Crystal data for 3: C44H70AlNO4, monoclinic, Cc, a = 23.50(1) {\AA}, b = 10.81(1) {\AA}, c= 19.37(1) {\AA}, β= 122.25(3)°, V = 4162(2) {\AA}, Z = 4.",
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T1 - Synthesis and Structure of Alkoxy- and (Aryloxy)alanes. Observation of a Ring-Opening Reaction Involving Tetrahydrofuran

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AU - Gladfelter, Wayne L

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N2 - Dihydrogen elimination from aluminum hydrides and alcohols was used to produce new alkoxide and aryloxide complexes. Dimethylethylamine-alane (DMEAA) reacted with 2 equiv of 2,6-diisopropylphenol (DIPH) in THF at -78 °C to give (DIP)2:A1H·2THF (1) in 94% yield. It was characterized by NMR, IR, MS. and X-ray crystallography and found to be trigonal bipyramidal with both axial sites occupied by THF. Crystal data for 1: C32H51AlO4, monoclinic, C2/c, a = 21.37(1) Å, b = 9.324(3) Å, c = 15.30(1) Å, β = 94.16(5)°, V = 3040(5)Å3, Z = 4. DMEAA reacted with 2 equiv of triphenylcarbinol, Ph3COH, in THF at -78 °C to give (Ph3CO)2AIH· THF (2) in 42% yield. The lower coordination number was attributed to the larger cone angle of the ligand. Crystal data for 2: C42H39AlO3, triclinic, P1̄, a = 8.482(1) Å, b = 9.067(1) Å, c = 23.59(1)°, α = 90.919(1)°, β = 92.624(1)°, γ = 116.093(1)°, V = 1626.2(2) Å3, Z = 2. Three equivalents of DIPH in THF reacted with DMEAA at -78 °C to form the unexpected compound (DIP)3(THF)(NMe2Et)Al (3) in 89% yield. Both solution spectroscopic and X-ray crystallographic data established that THF underwent a ring-opening reaction. Crystal data for 3: C44H70AlNO4, monoclinic, Cc, a = 23.50(1) Å, b = 10.81(1) Å, c= 19.37(1) Å, β= 122.25(3)°, V = 4162(2) Å, Z = 4.

AB - Dihydrogen elimination from aluminum hydrides and alcohols was used to produce new alkoxide and aryloxide complexes. Dimethylethylamine-alane (DMEAA) reacted with 2 equiv of 2,6-diisopropylphenol (DIPH) in THF at -78 °C to give (DIP)2:A1H·2THF (1) in 94% yield. It was characterized by NMR, IR, MS. and X-ray crystallography and found to be trigonal bipyramidal with both axial sites occupied by THF. Crystal data for 1: C32H51AlO4, monoclinic, C2/c, a = 21.37(1) Å, b = 9.324(3) Å, c = 15.30(1) Å, β = 94.16(5)°, V = 3040(5)Å3, Z = 4. DMEAA reacted with 2 equiv of triphenylcarbinol, Ph3COH, in THF at -78 °C to give (Ph3CO)2AIH· THF (2) in 42% yield. The lower coordination number was attributed to the larger cone angle of the ligand. Crystal data for 2: C42H39AlO3, triclinic, P1̄, a = 8.482(1) Å, b = 9.067(1) Å, c = 23.59(1)°, α = 90.919(1)°, β = 92.624(1)°, γ = 116.093(1)°, V = 1626.2(2) Å3, Z = 2. Three equivalents of DIPH in THF reacted with DMEAA at -78 °C to form the unexpected compound (DIP)3(THF)(NMe2Et)Al (3) in 89% yield. Both solution spectroscopic and X-ray crystallographic data established that THF underwent a ring-opening reaction. Crystal data for 3: C44H70AlNO4, monoclinic, Cc, a = 23.50(1) Å, b = 10.81(1) Å, c= 19.37(1) Å, β= 122.25(3)°, V = 4162(2) Å, Z = 4.

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