properties of borane, the bh molecule - mitweb.mit.edu/5.03/www/readings/electron_deficient/... ·...
TRANSCRIPT
![Page 1: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/1.jpg)
![Page 2: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/2.jpg)
Properties of Borane, the BH3 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
5.03 Inorganic Chemistry
![Page 3: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/3.jpg)
Borane Exists as a Dimer: Diborane
Diborane, B2H6, is a colorless gas forming explosive mixtureswith air
Diborane is endothermic with ∆H◦f = 36 kJ/mol
Despite this thermodynamic stability, diborane is kineticallynot so reactive but takes place in many reactions involvingloss of H2
Industrial synthesis: 8 BF3 + 6 LiH −→ B2H6 + 6 LiBF4
Convenient laboratory synthesis: 2 NaBH4 + I2 −→ 2 NaI +B2H6 + H2
5.03 Inorganic Chemistry
![Page 4: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/4.jpg)
Borane Exists as a Dimer: Diborane
Diborane, B2H6, is a colorless gas forming explosive mixtureswith air
Diborane is endothermic with ∆H◦f = 36 kJ/mol
Despite this thermodynamic stability, diborane is kineticallynot so reactive but takes place in many reactions involvingloss of H2
Industrial synthesis: 8 BF3 + 6 LiH −→ B2H6 + 6 LiBF4
Convenient laboratory synthesis: 2 NaBH4 + I2 −→ 2 NaI +B2H6 + H2
5.03 Inorganic Chemistry
![Page 5: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/5.jpg)
Borane Exists as a Dimer: Diborane
Diborane, B2H6, is a colorless gas forming explosive mixtureswith air
Diborane is endothermic with ∆H◦f = 36 kJ/mol
Despite this thermodynamic stability, diborane is kineticallynot so reactive but takes place in many reactions involvingloss of H2
Industrial synthesis: 8 BF3 + 6 LiH −→ B2H6 + 6 LiBF4
Convenient laboratory synthesis: 2 NaBH4 + I2 −→ 2 NaI +B2H6 + H2
5.03 Inorganic Chemistry
![Page 6: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/6.jpg)
Borane Exists as a Dimer: Diborane
Diborane, B2H6, is a colorless gas forming explosive mixtureswith air
Diborane is endothermic with ∆H◦f = 36 kJ/mol
Despite this thermodynamic stability, diborane is kineticallynot so reactive but takes place in many reactions involvingloss of H2
Industrial synthesis: 8 BF3 + 6 LiH −→ B2H6 + 6 LiBF4
Convenient laboratory synthesis: 2 NaBH4 + I2 −→ 2 NaI +B2H6 + H2
5.03 Inorganic Chemistry
![Page 7: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/7.jpg)
Borane Exists as a Dimer: Diborane
Diborane, B2H6, is a colorless gas forming explosive mixtureswith air
Diborane is endothermic with ∆H◦f = 36 kJ/mol
Despite this thermodynamic stability, diborane is kineticallynot so reactive but takes place in many reactions involvingloss of H2
Industrial synthesis: 8 BF3 + 6 LiH −→ B2H6 + 6 LiBF4
Convenient laboratory synthesis: 2 NaBH4 + I2 −→ 2 NaI +B2H6 + H2
5.03 Inorganic Chemistry
![Page 8: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/8.jpg)
Borane Exists as a Dimer: Diborane
Alfred Stock pioneered the chemistry of the boron hydridesusing vacuum-line techniques
Stock proposed an ethane-like structure for diborane
S. H. Bauer in 1937 reported electron diffractionmeasurements interpreted (DOI: 10.1021/ja01285a041) insupport of the ethane-like structure
The ethane-like structure required resonance structures withone-electron bonds
5.03 Inorganic Chemistry
![Page 9: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/9.jpg)
Borane Exists as a Dimer: Diborane
Alfred Stock pioneered the chemistry of the boron hydridesusing vacuum-line techniques
Stock proposed an ethane-like structure for diborane
S. H. Bauer in 1937 reported electron diffractionmeasurements interpreted (DOI: 10.1021/ja01285a041) insupport of the ethane-like structure
The ethane-like structure required resonance structures withone-electron bonds
5.03 Inorganic Chemistry
![Page 10: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/10.jpg)
Borane Exists as a Dimer: Diborane
Alfred Stock pioneered the chemistry of the boron hydridesusing vacuum-line techniques
Stock proposed an ethane-like structure for diborane
S. H. Bauer in 1937 reported electron diffractionmeasurements interpreted (DOI: 10.1021/ja01285a041) insupport of the ethane-like structure
The ethane-like structure required resonance structures withone-electron bonds
5.03 Inorganic Chemistry
![Page 11: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/11.jpg)
Borane Exists as a Dimer: Diborane
Alfred Stock pioneered the chemistry of the boron hydridesusing vacuum-line techniques
Stock proposed an ethane-like structure for diborane
S. H. Bauer in 1937 reported electron diffractionmeasurements interpreted (DOI: 10.1021/ja01285a041) insupport of the ethane-like structure
The ethane-like structure required resonance structures withone-electron bonds
5.03 Inorganic Chemistry
![Page 12: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/12.jpg)
Borane Exists as a Dimer: Diborane
1943 (DOI: 10.1039/JR9430000250) undergraduate studentH. C. Longuet-Higgins (Balliol College, Oxford) and R. P. Bellproposed B-H-B bridge bonds instead with a D2h symmetrystructure
In 1941 a U. of Chicago chemistry professor Schlesingerworking on the Manhattan project wrote a letter to LinusPauling suggesting the same structure with B-H-B bridgebonds (A Diborane Story, Pierre Laszlo, ACIE 2000, 39,2071); Pauling responded unfavorably
Mulliken weighed in (1947) with an MO analysis favoring theD2h structure because of agreement with electronic absorptionspectra
Price interpreted the IR data in terms of the D2h structureand gave assignments
Shoolery reported clinching NMR data in 1955
5.03 Inorganic Chemistry
![Page 13: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/13.jpg)
Borane Exists as a Dimer: Diborane
1943 (DOI: 10.1039/JR9430000250) undergraduate studentH. C. Longuet-Higgins (Balliol College, Oxford) and R. P. Bellproposed B-H-B bridge bonds instead with a D2h symmetrystructure
In 1941 a U. of Chicago chemistry professor Schlesingerworking on the Manhattan project wrote a letter to LinusPauling suggesting the same structure with B-H-B bridgebonds (A Diborane Story, Pierre Laszlo, ACIE 2000, 39,2071); Pauling responded unfavorably
Mulliken weighed in (1947) with an MO analysis favoring theD2h structure because of agreement with electronic absorptionspectra
Price interpreted the IR data in terms of the D2h structureand gave assignments
Shoolery reported clinching NMR data in 1955
5.03 Inorganic Chemistry
![Page 14: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/14.jpg)
Borane Exists as a Dimer: Diborane
1943 (DOI: 10.1039/JR9430000250) undergraduate studentH. C. Longuet-Higgins (Balliol College, Oxford) and R. P. Bellproposed B-H-B bridge bonds instead with a D2h symmetrystructure
In 1941 a U. of Chicago chemistry professor Schlesingerworking on the Manhattan project wrote a letter to LinusPauling suggesting the same structure with B-H-B bridgebonds (A Diborane Story, Pierre Laszlo, ACIE 2000, 39,2071); Pauling responded unfavorably
Mulliken weighed in (1947) with an MO analysis favoring theD2h structure because of agreement with electronic absorptionspectra
Price interpreted the IR data in terms of the D2h structureand gave assignments
Shoolery reported clinching NMR data in 1955
5.03 Inorganic Chemistry
![Page 15: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/15.jpg)
Borane Exists as a Dimer: Diborane
1943 (DOI: 10.1039/JR9430000250) undergraduate studentH. C. Longuet-Higgins (Balliol College, Oxford) and R. P. Bellproposed B-H-B bridge bonds instead with a D2h symmetrystructure
In 1941 a U. of Chicago chemistry professor Schlesingerworking on the Manhattan project wrote a letter to LinusPauling suggesting the same structure with B-H-B bridgebonds (A Diborane Story, Pierre Laszlo, ACIE 2000, 39,2071); Pauling responded unfavorably
Mulliken weighed in (1947) with an MO analysis favoring theD2h structure because of agreement with electronic absorptionspectra
Price interpreted the IR data in terms of the D2h structureand gave assignments
Shoolery reported clinching NMR data in 1955
5.03 Inorganic Chemistry
![Page 16: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/16.jpg)
Borane Exists as a Dimer: Diborane
1943 (DOI: 10.1039/JR9430000250) undergraduate studentH. C. Longuet-Higgins (Balliol College, Oxford) and R. P. Bellproposed B-H-B bridge bonds instead with a D2h symmetrystructure
In 1941 a U. of Chicago chemistry professor Schlesingerworking on the Manhattan project wrote a letter to LinusPauling suggesting the same structure with B-H-B bridgebonds (A Diborane Story, Pierre Laszlo, ACIE 2000, 39,2071); Pauling responded unfavorably
Mulliken weighed in (1947) with an MO analysis favoring theD2h structure because of agreement with electronic absorptionspectra
Price interpreted the IR data in terms of the D2h structureand gave assignments
Shoolery reported clinching NMR data in 1955
5.03 Inorganic Chemistry
![Page 17: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/17.jpg)
Structure for the B2H6 MoleculeGraphic from Price, 1948, DOI: 10.1063/1.1747028
5.03 Inorganic Chemistry
![Page 18: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/18.jpg)
Structure for the B2H6 MoleculeA different way of writing the bridge bonds
H BH HB H
H
H
5.03 Inorganic Chemistry
![Page 19: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/19.jpg)
![Page 20: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/20.jpg)
Borohydride Ion [BH4]− has Td Symmetry
-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.01H NMR (ppm)
-0.8
1-0
.71
-0.6
4-0
.61
-0.5
7-0
.50
-0.4
4-0
.41
-0.3
7-0
.30
-0.2
0
1.93
1.94
1.95
1.95
CD3CN
NaBH4
5.03 Inorganic Chemistry
![Page 21: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/21.jpg)
MO Calculations on the B2H6 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
This is one of the four terminal 2c-2e B-H bonds
5.03 Inorganic Chemistry
![Page 22: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/22.jpg)
MO Calculations on the B2H6 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
This is one of the four terminal 2c-2e B-H bonds
5.03 Inorganic Chemistry
![Page 23: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/23.jpg)
MO Calculations on the B2H6 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
This is one of the two 3c-2e B-H bridge bonds
5.03 Inorganic Chemistry
![Page 24: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/24.jpg)
MO Calculations on the B2H6 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
This is one of the two 3c-2e B-H bridge bonds
5.03 Inorganic Chemistry
![Page 25: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/25.jpg)
Resonance Structures for the B2H6 MoleculeNatural Bond Orbital (NBO) analysis following MO calculation
5.03 Inorganic Chemistry
![Page 26: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/26.jpg)
![Page 27: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/27.jpg)
Reaction of Borane THF Adduct with CO2Mizuta et al. Organometallics, 2014, 33, pp 6692–6695 DOI: 10.1021/om5008488
The reaction between commercially available borane solutionsand CO2 had not been reported!
The product of this reaction is called trimethoxyboroxine, withCO2 reduced to the level of methanol
5.03 Inorganic Chemistry
![Page 28: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/28.jpg)
Reaction of Borane THF Adduct with CO2Mizuta et al. Organometallics, 2014, 33, pp 6692–6695 DOI: 10.1021/om5008488
The reaction between commercially available borane solutionsand CO2 had not been reported!
The product of this reaction is called trimethoxyboroxine, withCO2 reduced to the level of methanol
5.03 Inorganic Chemistry
![Page 29: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/29.jpg)
Reaction of Borane THF Adduct with CO2Mizuta et al. Organometallics, 2014, 33, pp 6692–6695 DOI: 10.1021/om5008488
The reaction between commercially available borane solutionsand CO2 had not been reported!
The product of this reaction is called trimethoxyboroxine, withCO2 reduced to the level of methanol
5.03 Inorganic Chemistry
![Page 30: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/30.jpg)
Donor-Acceptor BondsTypically written with an arrow or with a line and formal charges
A donor-acceptor bond can be written this way: Me2O:→BH3
Alternatively it can be written this way: Me2O+–B−H3
A donor-acceptor complex forms with a Lewis base donatingan electron pair to a Lewis acid
5.03 Inorganic Chemistry
![Page 31: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/31.jpg)
Donor-Acceptor BondsTypically written with an arrow or with a line and formal charges
A donor-acceptor bond can be written this way: Me2O:→BH3
Alternatively it can be written this way: Me2O+–B−H3
A donor-acceptor complex forms with a Lewis base donatingan electron pair to a Lewis acid
5.03 Inorganic Chemistry
![Page 32: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/32.jpg)
Donor-Acceptor BondsTypically written with an arrow or with a line and formal charges
A donor-acceptor bond can be written this way: Me2O:→BH3
Alternatively it can be written this way: Me2O+–B−H3
A donor-acceptor complex forms with a Lewis base donatingan electron pair to a Lewis acid
5.03 Inorganic Chemistry
![Page 33: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/33.jpg)
Donor-Acceptor BondsTypically written with an arrow or with a line and formal charges
A donor-acceptor bond can be written this way: Me2O:→BH3
Alternatively it can be written this way: Me2O+–B−H3
A donor-acceptor complex forms with a Lewis base donatingan electron pair to a Lewis acid
5.03 Inorganic Chemistry
![Page 34: Properties of Borane, the BH Molecule - MITweb.mit.edu/5.03/www/readings/electron_deficient/... · 2015. 2. 27. · Natural Bond Orbital (NBO) analysis following MO calculation This](https://reader035.vdocuments.site/reader035/viewer/2022071103/5fdd4b4e879324343f6e81d8/html5/thumbnails/34.jpg)