Synthesis, structure, and bonding in zirconocene primary phosphide (PHR-), phosphinidene (PR2-), and phosphide (P3-) derivatives

Jianwei Ho, Roger Rousseau, Douglas W. Stephan

Research output: Contribution to journalArticle

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Abstract

The syntheses of the Zr primary phosphido complexes Cp2Zr(PH(C6H2-2,4,6-t-Bu3))Cl (1) and Cp2Zr(PH(C6H2-2,4,6-Me3))Cl (2) from the appropriate LiPHR and 1 equiv of Cp2ZrCl2 are described. In reactions of PH2(C6H2-2,4,6-Me3) or PH2SiMe3 with Cp2ZrHCl, the respective bridging-phosphinidene derivatives (Cp2ZrCl)22-PC6H 2-2,4,6-Me3) (3) and Cp2Zr(μ2-PSiPh3)(μ215-C5H4)ZrCpCl (4) are obtained. These products are planar at phosphorus, indicative of Zr-P π-bonding. Reaction of PH(C6H2-2,4,6-t-Bu3) with excess Cp2ZrHCl results in the formation of the planar, trinuclear phosphide complex (Cp2Zr)22-Cl)(μ 3-P)(ZrCp2Cl) (5). This species 5 is also generated from the addition of PH(C6H2-2,4,6-t-Bu3) to a mixture of Cp2ZrCl2 and Mg. The mixed-valent product 5 is paramagnetic, exhibiting an EPR spectrum typical of Zr(III)-P species. Under similar reaction conditions, but with prolonged exposure to Mg, the diamagnetic phosphide derivative (CpZr(μ215-C5H 4))33-P) (6) is obtained. In contrast to 5, the geometry at phosphorus in 6 is pyramidal. The terminal phosphinidene complexes Cp2Zr(P(C6H2-2,4,6-t-Bu3))(PMe 3) (7) and Cp2Zr(P(C6H2-Me3))(PMe3) (8) are generated via the reaction of 1 or 2 with KH and PMe3. The reaction mechanisms operative in the formation of these phosphinidene or phosphide complexes are discussed. MO calculations were performed on models of the terminal and bridging phosphinidene complexes as well as the planar and pyramidal trinuclear phosphide complexes. These studies provide insights regarding the structure and bonding in these compounds. Cumulatively, this work implies that phosphinidene species are generally highly reactive, exhibiting the ability to induce C-H and P-C activation. Crystallographic data are reported herein for compounds 1, 4, and 5. Compound 1: space group P21/a with a = 16.179(15) Å, b = 10.167(4) Å, c = 17.515(6) Å, β = 105.88(5)°, V = 2771(5) Å3, and Z = 4. Compound 4: space group P1 with a = 11.159(8) Å, b = 16.434(13) Å, c = 10.490(8) Å, α = 95.49(7)°, β = 111.63(6)°, γ = 71.73°, V = 2771(5) Å3, and Z = 2. Compound 5: space group P21/a with a = 15.683(6) Å, b = 10.379(4) Å, c = 17.250(6) Å, β = 93.28(4)°, V = 2802(2) Å3, and Z = 4.

Original languageEnglish
Pages (from-to)1918-1926
Number of pages9
JournalOrganometallics
Volume13
Issue number5
Publication statusPublished - 1994

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phosphides
Phosphorus
Derivatives
synthesis
Paramagnetic resonance
Chemical activation
phosphorus
Geometry
products
Zirconocene dichloride
activation
geometry

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis, structure, and bonding in zirconocene primary phosphide (PHR-), phosphinidene (PR2-), and phosphide (P3-) derivatives. / Ho, Jianwei; Rousseau, Roger; Stephan, Douglas W.

In: Organometallics, Vol. 13, No. 5, 1994, p. 1918-1926.

Research output: Contribution to journalArticle

@article{f989c08834ee4fec995e0f69afed07cb,
title = "Synthesis, structure, and bonding in zirconocene primary phosphide (PHR-), phosphinidene (PR2-), and phosphide (P3-) derivatives",
abstract = "The syntheses of the Zr primary phosphido complexes Cp2Zr(PH(C6H2-2,4,6-t-Bu3))Cl (1) and Cp2Zr(PH(C6H2-2,4,6-Me3))Cl (2) from the appropriate LiPHR and 1 equiv of Cp2ZrCl2 are described. In reactions of PH2(C6H2-2,4,6-Me3) or PH2SiMe3 with Cp2ZrHCl, the respective bridging-phosphinidene derivatives (Cp2ZrCl)2(μ2-PC6H 2-2,4,6-Me3) (3) and Cp2Zr(μ2-PSiPh3)(μ2-η 1:η5-C5H4)ZrCpCl (4) are obtained. These products are planar at phosphorus, indicative of Zr-P π-bonding. Reaction of PH(C6H2-2,4,6-t-Bu3) with excess Cp2ZrHCl results in the formation of the planar, trinuclear phosphide complex (Cp2Zr)2(μ2-Cl)(μ 3-P)(ZrCp2Cl) (5). This species 5 is also generated from the addition of PH(C6H2-2,4,6-t-Bu3) to a mixture of Cp2ZrCl2 and Mg. The mixed-valent product 5 is paramagnetic, exhibiting an EPR spectrum typical of Zr(III)-P species. Under similar reaction conditions, but with prolonged exposure to Mg, the diamagnetic phosphide derivative (CpZr(μ2-η1:η5-C5H 4))3(μ3-P) (6) is obtained. In contrast to 5, the geometry at phosphorus in 6 is pyramidal. The terminal phosphinidene complexes Cp2Zr(P(C6H2-2,4,6-t-Bu3))(PMe 3) (7) and Cp2Zr(P(C6H2-Me3))(PMe3) (8) are generated via the reaction of 1 or 2 with KH and PMe3. The reaction mechanisms operative in the formation of these phosphinidene or phosphide complexes are discussed. MO calculations were performed on models of the terminal and bridging phosphinidene complexes as well as the planar and pyramidal trinuclear phosphide complexes. These studies provide insights regarding the structure and bonding in these compounds. Cumulatively, this work implies that phosphinidene species are generally highly reactive, exhibiting the ability to induce C-H and P-C activation. Crystallographic data are reported herein for compounds 1, 4, and 5. Compound 1: space group P21/a with a = 16.179(15) {\AA}, b = 10.167(4) {\AA}, c = 17.515(6) {\AA}, β = 105.88(5)°, V = 2771(5) {\AA}3, and Z = 4. Compound 4: space group P1 with a = 11.159(8) {\AA}, b = 16.434(13) {\AA}, c = 10.490(8) {\AA}, α = 95.49(7)°, β = 111.63(6)°, γ = 71.73°, V = 2771(5) {\AA}3, and Z = 2. Compound 5: space group P21/a with a = 15.683(6) {\AA}, b = 10.379(4) {\AA}, c = 17.250(6) {\AA}, β = 93.28(4)°, V = 2802(2) {\AA}3, and Z = 4.",
author = "Jianwei Ho and Roger Rousseau and Stephan, {Douglas W.}",
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TY - JOUR

T1 - Synthesis, structure, and bonding in zirconocene primary phosphide (PHR-), phosphinidene (PR2-), and phosphide (P3-) derivatives

AU - Ho, Jianwei

AU - Rousseau, Roger

AU - Stephan, Douglas W.

PY - 1994

Y1 - 1994

N2 - The syntheses of the Zr primary phosphido complexes Cp2Zr(PH(C6H2-2,4,6-t-Bu3))Cl (1) and Cp2Zr(PH(C6H2-2,4,6-Me3))Cl (2) from the appropriate LiPHR and 1 equiv of Cp2ZrCl2 are described. In reactions of PH2(C6H2-2,4,6-Me3) or PH2SiMe3 with Cp2ZrHCl, the respective bridging-phosphinidene derivatives (Cp2ZrCl)2(μ2-PC6H 2-2,4,6-Me3) (3) and Cp2Zr(μ2-PSiPh3)(μ2-η 1:η5-C5H4)ZrCpCl (4) are obtained. These products are planar at phosphorus, indicative of Zr-P π-bonding. Reaction of PH(C6H2-2,4,6-t-Bu3) with excess Cp2ZrHCl results in the formation of the planar, trinuclear phosphide complex (Cp2Zr)2(μ2-Cl)(μ 3-P)(ZrCp2Cl) (5). This species 5 is also generated from the addition of PH(C6H2-2,4,6-t-Bu3) to a mixture of Cp2ZrCl2 and Mg. The mixed-valent product 5 is paramagnetic, exhibiting an EPR spectrum typical of Zr(III)-P species. Under similar reaction conditions, but with prolonged exposure to Mg, the diamagnetic phosphide derivative (CpZr(μ2-η1:η5-C5H 4))3(μ3-P) (6) is obtained. In contrast to 5, the geometry at phosphorus in 6 is pyramidal. The terminal phosphinidene complexes Cp2Zr(P(C6H2-2,4,6-t-Bu3))(PMe 3) (7) and Cp2Zr(P(C6H2-Me3))(PMe3) (8) are generated via the reaction of 1 or 2 with KH and PMe3. The reaction mechanisms operative in the formation of these phosphinidene or phosphide complexes are discussed. MO calculations were performed on models of the terminal and bridging phosphinidene complexes as well as the planar and pyramidal trinuclear phosphide complexes. These studies provide insights regarding the structure and bonding in these compounds. Cumulatively, this work implies that phosphinidene species are generally highly reactive, exhibiting the ability to induce C-H and P-C activation. Crystallographic data are reported herein for compounds 1, 4, and 5. Compound 1: space group P21/a with a = 16.179(15) Å, b = 10.167(4) Å, c = 17.515(6) Å, β = 105.88(5)°, V = 2771(5) Å3, and Z = 4. Compound 4: space group P1 with a = 11.159(8) Å, b = 16.434(13) Å, c = 10.490(8) Å, α = 95.49(7)°, β = 111.63(6)°, γ = 71.73°, V = 2771(5) Å3, and Z = 2. Compound 5: space group P21/a with a = 15.683(6) Å, b = 10.379(4) Å, c = 17.250(6) Å, β = 93.28(4)°, V = 2802(2) Å3, and Z = 4.

AB - The syntheses of the Zr primary phosphido complexes Cp2Zr(PH(C6H2-2,4,6-t-Bu3))Cl (1) and Cp2Zr(PH(C6H2-2,4,6-Me3))Cl (2) from the appropriate LiPHR and 1 equiv of Cp2ZrCl2 are described. In reactions of PH2(C6H2-2,4,6-Me3) or PH2SiMe3 with Cp2ZrHCl, the respective bridging-phosphinidene derivatives (Cp2ZrCl)2(μ2-PC6H 2-2,4,6-Me3) (3) and Cp2Zr(μ2-PSiPh3)(μ2-η 1:η5-C5H4)ZrCpCl (4) are obtained. These products are planar at phosphorus, indicative of Zr-P π-bonding. Reaction of PH(C6H2-2,4,6-t-Bu3) with excess Cp2ZrHCl results in the formation of the planar, trinuclear phosphide complex (Cp2Zr)2(μ2-Cl)(μ 3-P)(ZrCp2Cl) (5). This species 5 is also generated from the addition of PH(C6H2-2,4,6-t-Bu3) to a mixture of Cp2ZrCl2 and Mg. The mixed-valent product 5 is paramagnetic, exhibiting an EPR spectrum typical of Zr(III)-P species. Under similar reaction conditions, but with prolonged exposure to Mg, the diamagnetic phosphide derivative (CpZr(μ2-η1:η5-C5H 4))3(μ3-P) (6) is obtained. In contrast to 5, the geometry at phosphorus in 6 is pyramidal. The terminal phosphinidene complexes Cp2Zr(P(C6H2-2,4,6-t-Bu3))(PMe 3) (7) and Cp2Zr(P(C6H2-Me3))(PMe3) (8) are generated via the reaction of 1 or 2 with KH and PMe3. The reaction mechanisms operative in the formation of these phosphinidene or phosphide complexes are discussed. MO calculations were performed on models of the terminal and bridging phosphinidene complexes as well as the planar and pyramidal trinuclear phosphide complexes. These studies provide insights regarding the structure and bonding in these compounds. Cumulatively, this work implies that phosphinidene species are generally highly reactive, exhibiting the ability to induce C-H and P-C activation. Crystallographic data are reported herein for compounds 1, 4, and 5. Compound 1: space group P21/a with a = 16.179(15) Å, b = 10.167(4) Å, c = 17.515(6) Å, β = 105.88(5)°, V = 2771(5) Å3, and Z = 4. Compound 4: space group P1 with a = 11.159(8) Å, b = 16.434(13) Å, c = 10.490(8) Å, α = 95.49(7)°, β = 111.63(6)°, γ = 71.73°, V = 2771(5) Å3, and Z = 2. Compound 5: space group P21/a with a = 15.683(6) Å, b = 10.379(4) Å, c = 17.250(6) Å, β = 93.28(4)°, V = 2802(2) Å3, and Z = 4.

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