A planar tetracoordinate carbon and unusual bonding in an organodimetallic propynylidene complex arising from double C-H activation of an allene ligand

Jui-Hsien Huang, Jeffrey J. Luci, Ting Yu Lee, Dale C. Swenson, Jan H. Jensen, Louis Messerle

Research output: Contribution to journalArticle

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Abstract

Reduction of the organoditantalum allene complex (η-C5Me4R)2Ta2(μ-X)X3(μ-η13-C3H4) (R = Me (Cp*), Et; X = Cl, Br) with sodium amalgam leads to the propynylidene complex (η-C5Me4R)2Ta2(μ-H)2X2(μ-HCCCH) by a formal double 1,3-C-H activation of the allene ligand. The solid-state molecular structure contains a planar HCCCH ligand bridging, in parallel coordination mode, the two tantalum atoms, with the HCCCH and Ta atoms coplanar. Key structural features are a Ta-Ta distance of 2.8817(7) Å, propynylidene C-C-C angle of 153.7(13)°, C-C distance of 1.370(8) Å, Ta-C(central) distance of 2.194(9) Å, and Ta-C(terminal) distance of 1.970(9) Å. Molecular orbital calculations on the complex at the RHF/SBK(d) and B3LYP/LanL2dz levels of theory demonstrate that the propynylidene ligand is best viewed formally as an allenediylidene(4-) ligand bonded to two d0 tantalum atoms via two Ta=C(terminal) double bonds and an unusual three-center, two-electron bridge bond involving both tantalum atoms and a lone pair on the planar, tetracoordinate central carbon. There is no net Ta-Ta bonding based on the orbital analysis.

Original languageEnglish
Pages (from-to)1688-1689
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number7
DOIs
Publication statusPublished - 2003 Feb 15

Fingerprint

Tantalum
Carbon
Chemical activation
Ligands
Atoms
Mercury amalgams
Orbital calculations
Molecular orbitals
Molecular Structure
Molecular structure
Sodium
Electrons
propadiene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Huang, Jui-Hsien ; Luci, Jeffrey J. ; Lee, Ting Yu ; Swenson, Dale C. ; Jensen, Jan H. ; Messerle, Louis. / A planar tetracoordinate carbon and unusual bonding in an organodimetallic propynylidene complex arising from double C-H activation of an allene ligand. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 7. pp. 1688-1689.
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title = "A planar tetracoordinate carbon and unusual bonding in an organodimetallic propynylidene complex arising from double C-H activation of an allene ligand",
abstract = "Reduction of the organoditantalum allene complex (η-C5Me4R)2Ta2(μ-X)X3(μ-η1,η3-C3H4) (R = Me (Cp*), Et; X = Cl, Br) with sodium amalgam leads to the propynylidene complex (η-C5Me4R)2Ta2(μ-H)2X2(μ-HCCCH) by a formal double 1,3-C-H activation of the allene ligand. The solid-state molecular structure contains a planar HCCCH ligand bridging, in parallel coordination mode, the two tantalum atoms, with the HCCCH and Ta atoms coplanar. Key structural features are a Ta-Ta distance of 2.8817(7) {\AA}, propynylidene C-C-C angle of 153.7(13)°, C-C distance of 1.370(8) {\AA}, Ta-C(central) distance of 2.194(9) {\AA}, and Ta-C(terminal) distance of 1.970(9) {\AA}. Molecular orbital calculations on the complex at the RHF/SBK(d) and B3LYP/LanL2dz levels of theory demonstrate that the propynylidene ligand is best viewed formally as an allenediylidene(4-) ligand bonded to two d0 tantalum atoms via two Ta=C(terminal) double bonds and an unusual three-center, two-electron bridge bond involving both tantalum atoms and a lone pair on the planar, tetracoordinate central carbon. There is no net Ta-Ta bonding based on the orbital analysis.",
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A planar tetracoordinate carbon and unusual bonding in an organodimetallic propynylidene complex arising from double C-H activation of an allene ligand. / Huang, Jui-Hsien; Luci, Jeffrey J.; Lee, Ting Yu; Swenson, Dale C.; Jensen, Jan H.; Messerle, Louis.

In: Journal of the American Chemical Society, Vol. 125, No. 7, 15.02.2003, p. 1688-1689.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A planar tetracoordinate carbon and unusual bonding in an organodimetallic propynylidene complex arising from double C-H activation of an allene ligand

AU - Huang, Jui-Hsien

AU - Luci, Jeffrey J.

AU - Lee, Ting Yu

AU - Swenson, Dale C.

AU - Jensen, Jan H.

AU - Messerle, Louis

PY - 2003/2/15

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N2 - Reduction of the organoditantalum allene complex (η-C5Me4R)2Ta2(μ-X)X3(μ-η1,η3-C3H4) (R = Me (Cp*), Et; X = Cl, Br) with sodium amalgam leads to the propynylidene complex (η-C5Me4R)2Ta2(μ-H)2X2(μ-HCCCH) by a formal double 1,3-C-H activation of the allene ligand. The solid-state molecular structure contains a planar HCCCH ligand bridging, in parallel coordination mode, the two tantalum atoms, with the HCCCH and Ta atoms coplanar. Key structural features are a Ta-Ta distance of 2.8817(7) Å, propynylidene C-C-C angle of 153.7(13)°, C-C distance of 1.370(8) Å, Ta-C(central) distance of 2.194(9) Å, and Ta-C(terminal) distance of 1.970(9) Å. Molecular orbital calculations on the complex at the RHF/SBK(d) and B3LYP/LanL2dz levels of theory demonstrate that the propynylidene ligand is best viewed formally as an allenediylidene(4-) ligand bonded to two d0 tantalum atoms via two Ta=C(terminal) double bonds and an unusual three-center, two-electron bridge bond involving both tantalum atoms and a lone pair on the planar, tetracoordinate central carbon. There is no net Ta-Ta bonding based on the orbital analysis.

AB - Reduction of the organoditantalum allene complex (η-C5Me4R)2Ta2(μ-X)X3(μ-η1,η3-C3H4) (R = Me (Cp*), Et; X = Cl, Br) with sodium amalgam leads to the propynylidene complex (η-C5Me4R)2Ta2(μ-H)2X2(μ-HCCCH) by a formal double 1,3-C-H activation of the allene ligand. The solid-state molecular structure contains a planar HCCCH ligand bridging, in parallel coordination mode, the two tantalum atoms, with the HCCCH and Ta atoms coplanar. Key structural features are a Ta-Ta distance of 2.8817(7) Å, propynylidene C-C-C angle of 153.7(13)°, C-C distance of 1.370(8) Å, Ta-C(central) distance of 2.194(9) Å, and Ta-C(terminal) distance of 1.970(9) Å. Molecular orbital calculations on the complex at the RHF/SBK(d) and B3LYP/LanL2dz levels of theory demonstrate that the propynylidene ligand is best viewed formally as an allenediylidene(4-) ligand bonded to two d0 tantalum atoms via two Ta=C(terminal) double bonds and an unusual three-center, two-electron bridge bond involving both tantalum atoms and a lone pair on the planar, tetracoordinate central carbon. There is no net Ta-Ta bonding based on the orbital analysis.

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