Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications

Yasushi Nishihara, Kathryn J. Deck, Maoyu Shang, Thomas P. Fehlner, Brian S. Haggerty, Arnold L. Rheingold

Research output: Contribution to journalArticle

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Abstract

The reaction of [Cp*CoCl]2, Cp* = η5-C5Me5, with BH3·THF leads to the formation of nido-1-(η5-C5Me5)Co-2-(η 4-C5Me5H)CoB3H8, 1 (60%, monoclinic P21/n, a = 8.076(1), b = 20.359(2), c = 13.880(2) Å, β = 91.23(1)°, V = 2281.7(6) Å3, d(calcd) = 1.251g/cm3, Z = 4), and arachno-(η5-C5Me5)CoB4H 10, 2 (2-10%, monoclinic P21/c, a = 13.954(3), b = 14.185(4), c = 29.383(7) Å, β = 100.61(2)°, V = 5717(2) Å3, d(calcd) = 1.150 g/cm3, Z = 16) via the metastable paramagnetic intermediate [{(η5-C5Me5)Co}(BH3Cl)] 2, 9, with the coproduct BH2Cl. Heating 1 leads to nido-2,4-{(η5-C5Me5)Co}2B 3H7, 3 (80%, tetragonal P42/n, a = b = 23.440(4), c = 8.317(2) Å, V = 4570(1) Å3, d(calcd) = 1.244 g cm-3, Z = 8). The reaction of [Cp*CoCl]2 with LiBH4 leads to the formation of closo-2,3,4-{(η5-C5Me5)Co} 3B2H4, 4 (20%, rhombohedral, R3, a = 17.994 (1) Å, c = 15.986 (1) Å, V = 4477.3 Å3, d(calcd) = 1.347 g cm-3, Z = 6) and lesser amounts of closo-1,2,3-{(η5-C5Me5)Co} 3B3H5, 5 (triclinic, P1, a = 8.461 (2) Å, b = 10.718 (2) Å, c = 17.591 (4) Å, V = 1511.0 (8) Å3, d(calcd) = 1.363 g cm-3, Z = 2), and closo-1,2,3,6-{(η5-C5Me5)Co} 4B2H4, 6, via the sequential formation of the metastable intermediates [{(η5-C5Me5)Co}(BH4)] n, 7 (paramagnetic), and {(η5-C5Me5)Co}2B 2H6, 8 (diamagnetic). These results demonstrate that a labile metal precursor permits control of the number of metal atoms in the metallaborane and the characterization of unusual and metastable cobaltaboranes. A kinetic study of the conversion of 1 to 3, which involves the intramolecular dehydrogenation of a η4-C5Me5H ligand and skeletal rearrangement, is reported and the mechanistic implications for the origin of 1 are discussed.

Original languageEnglish
Pages (from-to)4510-4522
Number of pages13
JournalOrganometallics
Volume13
Issue number11
Publication statusPublished - 1994
Externally publishedYes

Fingerprint

Metals
Dehydrogenation
synthesis
dehydrogenation
Ligands
Heating
Atoms
metals
Kinetics
ligands
heating
kinetics
atoms
cobaltous chloride

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Nishihara, Y., Deck, K. J., Shang, M., Fehlner, T. P., Haggerty, B. S., & Rheingold, A. L. (1994). Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications. Organometallics, 13(11), 4510-4522.

Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications. / Nishihara, Yasushi; Deck, Kathryn J.; Shang, Maoyu; Fehlner, Thomas P.; Haggerty, Brian S.; Rheingold, Arnold L.

In: Organometallics, Vol. 13, No. 11, 1994, p. 4510-4522.

Research output: Contribution to journalArticle

Nishihara, Y, Deck, KJ, Shang, M, Fehlner, TP, Haggerty, BS & Rheingold, AL 1994, 'Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications', Organometallics, vol. 13, no. 11, pp. 4510-4522.
Nishihara, Yasushi ; Deck, Kathryn J. ; Shang, Maoyu ; Fehlner, Thomas P. ; Haggerty, Brian S. ; Rheingold, Arnold L. / Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications. In: Organometallics. 1994 ; Vol. 13, No. 11. pp. 4510-4522.
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title = "Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications",
abstract = "The reaction of [Cp*CoCl]2, Cp* = η5-C5Me5, with BH3·THF leads to the formation of nido-1-(η5-C5Me5)Co-2-(η 4-C5Me5H)CoB3H8, 1 (60{\%}, monoclinic P21/n, a = 8.076(1), b = 20.359(2), c = 13.880(2) {\AA}, β = 91.23(1)°, V = 2281.7(6) {\AA}3, d(calcd) = 1.251g/cm3, Z = 4), and arachno-(η5-C5Me5)CoB4H 10, 2 (2-10{\%}, monoclinic P21/c, a = 13.954(3), b = 14.185(4), c = 29.383(7) {\AA}, β = 100.61(2)°, V = 5717(2) {\AA}3, d(calcd) = 1.150 g/cm3, Z = 16) via the metastable paramagnetic intermediate [{(η5-C5Me5)Co}(BH3Cl)] 2, 9, with the coproduct BH2Cl. Heating 1 leads to nido-2,4-{(η5-C5Me5)Co}2B 3H7, 3 (80{\%}, tetragonal P42/n, a = b = 23.440(4), c = 8.317(2) {\AA}, V = 4570(1) {\AA}3, d(calcd) = 1.244 g cm-3, Z = 8). The reaction of [Cp*CoCl]2 with LiBH4 leads to the formation of closo-2,3,4-{(η5-C5Me5)Co} 3B2H4, 4 (20{\%}, rhombohedral, R3, a = 17.994 (1) {\AA}, c = 15.986 (1) {\AA}, V = 4477.3 {\AA}3, d(calcd) = 1.347 g cm-3, Z = 6) and lesser amounts of closo-1,2,3-{(η5-C5Me5)Co} 3B3H5, 5 (triclinic, P1, a = 8.461 (2) {\AA}, b = 10.718 (2) {\AA}, c = 17.591 (4) {\AA}, V = 1511.0 (8) {\AA}3, d(calcd) = 1.363 g cm-3, Z = 2), and closo-1,2,3,6-{(η5-C5Me5)Co} 4B2H4, 6, via the sequential formation of the metastable intermediates [{(η5-C5Me5)Co}(BH4)] n, 7 (paramagnetic), and {(η5-C5Me5)Co}2B 2H6, 8 (diamagnetic). These results demonstrate that a labile metal precursor permits control of the number of metal atoms in the metallaborane and the characterization of unusual and metastable cobaltaboranes. A kinetic study of the conversion of 1 to 3, which involves the intramolecular dehydrogenation of a η4-C5Me5H ligand and skeletal rearrangement, is reported and the mechanistic implications for the origin of 1 are discussed.",
author = "Yasushi Nishihara and Deck, {Kathryn J.} and Maoyu Shang and Fehlner, {Thomas P.} and Haggerty, {Brian S.} and Rheingold, {Arnold L.}",
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TY - JOUR

T1 - Synthesis of cobaltaborane clusters from [Cp*CoCl]2 and monoboranes. New structures and mechanistic implications

AU - Nishihara, Yasushi

AU - Deck, Kathryn J.

AU - Shang, Maoyu

AU - Fehlner, Thomas P.

AU - Haggerty, Brian S.

AU - Rheingold, Arnold L.

PY - 1994

Y1 - 1994

N2 - The reaction of [Cp*CoCl]2, Cp* = η5-C5Me5, with BH3·THF leads to the formation of nido-1-(η5-C5Me5)Co-2-(η 4-C5Me5H)CoB3H8, 1 (60%, monoclinic P21/n, a = 8.076(1), b = 20.359(2), c = 13.880(2) Å, β = 91.23(1)°, V = 2281.7(6) Å3, d(calcd) = 1.251g/cm3, Z = 4), and arachno-(η5-C5Me5)CoB4H 10, 2 (2-10%, monoclinic P21/c, a = 13.954(3), b = 14.185(4), c = 29.383(7) Å, β = 100.61(2)°, V = 5717(2) Å3, d(calcd) = 1.150 g/cm3, Z = 16) via the metastable paramagnetic intermediate [{(η5-C5Me5)Co}(BH3Cl)] 2, 9, with the coproduct BH2Cl. Heating 1 leads to nido-2,4-{(η5-C5Me5)Co}2B 3H7, 3 (80%, tetragonal P42/n, a = b = 23.440(4), c = 8.317(2) Å, V = 4570(1) Å3, d(calcd) = 1.244 g cm-3, Z = 8). The reaction of [Cp*CoCl]2 with LiBH4 leads to the formation of closo-2,3,4-{(η5-C5Me5)Co} 3B2H4, 4 (20%, rhombohedral, R3, a = 17.994 (1) Å, c = 15.986 (1) Å, V = 4477.3 Å3, d(calcd) = 1.347 g cm-3, Z = 6) and lesser amounts of closo-1,2,3-{(η5-C5Me5)Co} 3B3H5, 5 (triclinic, P1, a = 8.461 (2) Å, b = 10.718 (2) Å, c = 17.591 (4) Å, V = 1511.0 (8) Å3, d(calcd) = 1.363 g cm-3, Z = 2), and closo-1,2,3,6-{(η5-C5Me5)Co} 4B2H4, 6, via the sequential formation of the metastable intermediates [{(η5-C5Me5)Co}(BH4)] n, 7 (paramagnetic), and {(η5-C5Me5)Co}2B 2H6, 8 (diamagnetic). These results demonstrate that a labile metal precursor permits control of the number of metal atoms in the metallaborane and the characterization of unusual and metastable cobaltaboranes. A kinetic study of the conversion of 1 to 3, which involves the intramolecular dehydrogenation of a η4-C5Me5H ligand and skeletal rearrangement, is reported and the mechanistic implications for the origin of 1 are discussed.

AB - The reaction of [Cp*CoCl]2, Cp* = η5-C5Me5, with BH3·THF leads to the formation of nido-1-(η5-C5Me5)Co-2-(η 4-C5Me5H)CoB3H8, 1 (60%, monoclinic P21/n, a = 8.076(1), b = 20.359(2), c = 13.880(2) Å, β = 91.23(1)°, V = 2281.7(6) Å3, d(calcd) = 1.251g/cm3, Z = 4), and arachno-(η5-C5Me5)CoB4H 10, 2 (2-10%, monoclinic P21/c, a = 13.954(3), b = 14.185(4), c = 29.383(7) Å, β = 100.61(2)°, V = 5717(2) Å3, d(calcd) = 1.150 g/cm3, Z = 16) via the metastable paramagnetic intermediate [{(η5-C5Me5)Co}(BH3Cl)] 2, 9, with the coproduct BH2Cl. Heating 1 leads to nido-2,4-{(η5-C5Me5)Co}2B 3H7, 3 (80%, tetragonal P42/n, a = b = 23.440(4), c = 8.317(2) Å, V = 4570(1) Å3, d(calcd) = 1.244 g cm-3, Z = 8). The reaction of [Cp*CoCl]2 with LiBH4 leads to the formation of closo-2,3,4-{(η5-C5Me5)Co} 3B2H4, 4 (20%, rhombohedral, R3, a = 17.994 (1) Å, c = 15.986 (1) Å, V = 4477.3 Å3, d(calcd) = 1.347 g cm-3, Z = 6) and lesser amounts of closo-1,2,3-{(η5-C5Me5)Co} 3B3H5, 5 (triclinic, P1, a = 8.461 (2) Å, b = 10.718 (2) Å, c = 17.591 (4) Å, V = 1511.0 (8) Å3, d(calcd) = 1.363 g cm-3, Z = 2), and closo-1,2,3,6-{(η5-C5Me5)Co} 4B2H4, 6, via the sequential formation of the metastable intermediates [{(η5-C5Me5)Co}(BH4)] n, 7 (paramagnetic), and {(η5-C5Me5)Co}2B 2H6, 8 (diamagnetic). These results demonstrate that a labile metal precursor permits control of the number of metal atoms in the metallaborane and the characterization of unusual and metastable cobaltaboranes. A kinetic study of the conversion of 1 to 3, which involves the intramolecular dehydrogenation of a η4-C5Me5H ligand and skeletal rearrangement, is reported and the mechanistic implications for the origin of 1 are discussed.

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