Germanium(II)-Inserted η5-closo-Germacarboranes and Their Donor-Acceptor Complexes. Crystal Structure of 1-Ge(C10H8N2)-2,3-(Me3Si)2-2,3-C2B4H4

Narayan S. Hosmane, M. Safiqul Islam, Brian Pinkston, Upali Siriwardane, John J. Banewicz, John A. Maguire

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The reaction of GeCl4 with the nido-carborane dianionic salts NaLi[(Me3Si)(R)C2B4H4] (R = SiMe3, Me, or H) in a molar ratio of 1:2 in THF produced closo-1-GeII-2,3-(SiMe3)2-2,3-C2B4H4(I), closo-1-GeII-2-(SiMe3)-3-(Me)-2,3-C2B4H4(II), and closo-1-GeII-2-(SiMe3)-2,3-C2B4H5(III) as air-sensitive, pale yellow liquids, in 36, 49, and 23% yields, respectively. In addition to the corresponding neutral nido-carborane precursors, the Ge(IV)-inserted derivatives of commo-bis(germacarborane), [(Me3Si)(R)C2B4H4]2GeIV, were also produced in 9.0, 7.4, and 9.5% yields when R = SiMe3, Me, and H, respectively. The closo-germacarboranes I, II, and III react slowly with 2,2'-bipyridine in benzene to form the electron donor-acceptor complexes l-GeII-(C10H8N2)-2,3-(SiMe3)2-2,3-C2B4H4 (IV), 1-GeII(C10H8N2)-2-(SiMe3)-3-(Me)-2,3-C2B4H4(V), and 1-GeII-(C10H8N2)-2-(SiMe3)-2,3-C2B4H5(VI) in 73, 42, and 48% yields, respectively. Both the visible/UV and 11B NMR spectroscopic results on IV-VI indicate that at least two different kinetic processes are taking place: a slow formation of the bipyridine-germacarborane adduct, followed by a rapid intraor intermolecular process which causes all the basal and apical boron atoms to become equivalent on an NMR time scale. The X-ray crystal structure of IV shows an extreme displacement of the germanium from the centroidal position above the C2B3 face in its distorted pentagonal-bipyramidal geometry with the Lewis base tilted significantly away from the cage carbons. The slippage of the apical germanium is such that it could be considered as η2-bonded to the C2B3 face of the carborane cage. Although some similarities between the closo-germacarborane and the closo-stannacarborane systems exist, the donoracceptor complexes of the two metallacarboranes seem to be quite different. Compound IV crystallizes in the monoclinic space group P21/n with a = 7.102 (5) Å, b = 34.61 (2) Å, c = 9.774 (4) Å, β = 102.55 (4)°, U = 2345 (2) Å3, and Z = 4. Full-matrix least-squares refinement converged at R = 0.040 and Rw= 0.038.

Original languageEnglish (US)
Pages (from-to)2340-2345
Number of pages6
JournalOrganometallics
Volume7
Issue number11
DOIs
StatePublished - Jan 1 1988
Externally publishedYes

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Germanium
carborane
germanium
Crystal structure
Lewis Bases
Nuclear magnetic resonance
2,2'-Dipyridyl
crystal structure
Boron
Benzene
Lewis base
nuclear magnetic resonance
Carbon
Salts
Derivatives
X rays
Atoms
adducts
Kinetics
Geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Germanium(II)-Inserted η5-closo-Germacarboranes and Their Donor-Acceptor Complexes. Crystal Structure of 1-Ge(C10H8N2)-2,3-(Me3Si)2-2,3-C2B4H4 . / Hosmane, Narayan S.; Islam, M. Safiqul; Pinkston, Brian; Siriwardane, Upali; Banewicz, John J.; Maguire, John A.

In: Organometallics, Vol. 7, No. 11, 01.01.1988, p. 2340-2345.

Research output: Contribution to journalArticle

Hosmane, Narayan S. ; Islam, M. Safiqul ; Pinkston, Brian ; Siriwardane, Upali ; Banewicz, John J. ; Maguire, John A. / Germanium(II)-Inserted η5-closo-Germacarboranes and Their Donor-Acceptor Complexes. Crystal Structure of 1-Ge(C10H8N2)-2,3-(Me3Si)2-2,3-C2B4H4 In: Organometallics. 1988 ; Vol. 7, No. 11. pp. 2340-2345.
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title = "Germanium(II)-Inserted η5-closo-Germacarboranes and Their Donor-Acceptor Complexes. Crystal Structure of 1-Ge(C10H8N2)-2,3-(Me3Si)2-2,3-C2B4H4",
abstract = "The reaction of GeCl4 with the nido-carborane dianionic salts NaLi[(Me3Si)(R)C2B4H4] (R = SiMe3, Me, or H) in a molar ratio of 1:2 in THF produced closo-1-GeII-2,3-(SiMe3)2-2,3-C2B4H4(I), closo-1-GeII-2-(SiMe3)-3-(Me)-2,3-C2B4H4(II), and closo-1-GeII-2-(SiMe3)-2,3-C2B4H5(III) as air-sensitive, pale yellow liquids, in 36, 49, and 23{\%} yields, respectively. In addition to the corresponding neutral nido-carborane precursors, the Ge(IV)-inserted derivatives of commo-bis(germacarborane), [(Me3Si)(R)C2B4H4]2GeIV, were also produced in 9.0, 7.4, and 9.5{\%} yields when R = SiMe3, Me, and H, respectively. The closo-germacarboranes I, II, and III react slowly with 2,2'-bipyridine in benzene to form the electron donor-acceptor complexes l-GeII-(C10H8N2)-2,3-(SiMe3)2-2,3-C2B4H4 (IV), 1-GeII(C10H8N2)-2-(SiMe3)-3-(Me)-2,3-C2B4H4(V), and 1-GeII-(C10H8N2)-2-(SiMe3)-2,3-C2B4H5(VI) in 73, 42, and 48{\%} yields, respectively. Both the visible/UV and 11B NMR spectroscopic results on IV-VI indicate that at least two different kinetic processes are taking place: a slow formation of the bipyridine-germacarborane adduct, followed by a rapid intraor intermolecular process which causes all the basal and apical boron atoms to become equivalent on an NMR time scale. The X-ray crystal structure of IV shows an extreme displacement of the germanium from the centroidal position above the C2B3 face in its distorted pentagonal-bipyramidal geometry with the Lewis base tilted significantly away from the cage carbons. The slippage of the apical germanium is such that it could be considered as η2-bonded to the C2B3 face of the carborane cage. Although some similarities between the closo-germacarborane and the closo-stannacarborane systems exist, the donoracceptor complexes of the two metallacarboranes seem to be quite different. Compound IV crystallizes in the monoclinic space group P21/n with a = 7.102 (5) {\AA}, b = 34.61 (2) {\AA}, c = 9.774 (4) {\AA}, β = 102.55 (4)°, U = 2345 (2) {\AA}3, and Z = 4. Full-matrix least-squares refinement converged at R = 0.040 and Rw= 0.038.",
author = "Hosmane, {Narayan S.} and Islam, {M. Safiqul} and Brian Pinkston and Upali Siriwardane and Banewicz, {John J.} and Maguire, {John A.}",
year = "1988",
month = "1",
day = "1",
doi = "10.1021/om00101a014",
language = "English (US)",
volume = "7",
pages = "2340--2345",
journal = "Organometallics",
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TY - JOUR

T1 - Germanium(II)-Inserted η5-closo-Germacarboranes and Their Donor-Acceptor Complexes. Crystal Structure of 1-Ge(C10H8N2)-2,3-(Me3Si)2-2,3-C2B4H4

AU - Hosmane, Narayan S.

AU - Islam, M. Safiqul

AU - Pinkston, Brian

AU - Siriwardane, Upali

AU - Banewicz, John J.

AU - Maguire, John A.

PY - 1988/1/1

Y1 - 1988/1/1

N2 - The reaction of GeCl4 with the nido-carborane dianionic salts NaLi[(Me3Si)(R)C2B4H4] (R = SiMe3, Me, or H) in a molar ratio of 1:2 in THF produced closo-1-GeII-2,3-(SiMe3)2-2,3-C2B4H4(I), closo-1-GeII-2-(SiMe3)-3-(Me)-2,3-C2B4H4(II), and closo-1-GeII-2-(SiMe3)-2,3-C2B4H5(III) as air-sensitive, pale yellow liquids, in 36, 49, and 23% yields, respectively. In addition to the corresponding neutral nido-carborane precursors, the Ge(IV)-inserted derivatives of commo-bis(germacarborane), [(Me3Si)(R)C2B4H4]2GeIV, were also produced in 9.0, 7.4, and 9.5% yields when R = SiMe3, Me, and H, respectively. The closo-germacarboranes I, II, and III react slowly with 2,2'-bipyridine in benzene to form the electron donor-acceptor complexes l-GeII-(C10H8N2)-2,3-(SiMe3)2-2,3-C2B4H4 (IV), 1-GeII(C10H8N2)-2-(SiMe3)-3-(Me)-2,3-C2B4H4(V), and 1-GeII-(C10H8N2)-2-(SiMe3)-2,3-C2B4H5(VI) in 73, 42, and 48% yields, respectively. Both the visible/UV and 11B NMR spectroscopic results on IV-VI indicate that at least two different kinetic processes are taking place: a slow formation of the bipyridine-germacarborane adduct, followed by a rapid intraor intermolecular process which causes all the basal and apical boron atoms to become equivalent on an NMR time scale. The X-ray crystal structure of IV shows an extreme displacement of the germanium from the centroidal position above the C2B3 face in its distorted pentagonal-bipyramidal geometry with the Lewis base tilted significantly away from the cage carbons. The slippage of the apical germanium is such that it could be considered as η2-bonded to the C2B3 face of the carborane cage. Although some similarities between the closo-germacarborane and the closo-stannacarborane systems exist, the donoracceptor complexes of the two metallacarboranes seem to be quite different. Compound IV crystallizes in the monoclinic space group P21/n with a = 7.102 (5) Å, b = 34.61 (2) Å, c = 9.774 (4) Å, β = 102.55 (4)°, U = 2345 (2) Å3, and Z = 4. Full-matrix least-squares refinement converged at R = 0.040 and Rw= 0.038.

AB - The reaction of GeCl4 with the nido-carborane dianionic salts NaLi[(Me3Si)(R)C2B4H4] (R = SiMe3, Me, or H) in a molar ratio of 1:2 in THF produced closo-1-GeII-2,3-(SiMe3)2-2,3-C2B4H4(I), closo-1-GeII-2-(SiMe3)-3-(Me)-2,3-C2B4H4(II), and closo-1-GeII-2-(SiMe3)-2,3-C2B4H5(III) as air-sensitive, pale yellow liquids, in 36, 49, and 23% yields, respectively. In addition to the corresponding neutral nido-carborane precursors, the Ge(IV)-inserted derivatives of commo-bis(germacarborane), [(Me3Si)(R)C2B4H4]2GeIV, were also produced in 9.0, 7.4, and 9.5% yields when R = SiMe3, Me, and H, respectively. The closo-germacarboranes I, II, and III react slowly with 2,2'-bipyridine in benzene to form the electron donor-acceptor complexes l-GeII-(C10H8N2)-2,3-(SiMe3)2-2,3-C2B4H4 (IV), 1-GeII(C10H8N2)-2-(SiMe3)-3-(Me)-2,3-C2B4H4(V), and 1-GeII-(C10H8N2)-2-(SiMe3)-2,3-C2B4H5(VI) in 73, 42, and 48% yields, respectively. Both the visible/UV and 11B NMR spectroscopic results on IV-VI indicate that at least two different kinetic processes are taking place: a slow formation of the bipyridine-germacarborane adduct, followed by a rapid intraor intermolecular process which causes all the basal and apical boron atoms to become equivalent on an NMR time scale. The X-ray crystal structure of IV shows an extreme displacement of the germanium from the centroidal position above the C2B3 face in its distorted pentagonal-bipyramidal geometry with the Lewis base tilted significantly away from the cage carbons. The slippage of the apical germanium is such that it could be considered as η2-bonded to the C2B3 face of the carborane cage. Although some similarities between the closo-germacarborane and the closo-stannacarborane systems exist, the donoracceptor complexes of the two metallacarboranes seem to be quite different. Compound IV crystallizes in the monoclinic space group P21/n with a = 7.102 (5) Å, b = 34.61 (2) Å, c = 9.774 (4) Å, β = 102.55 (4)°, U = 2345 (2) Å3, and Z = 4. Full-matrix least-squares refinement converged at R = 0.040 and Rw= 0.038.

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