Synthesis and properfies of a new class of highly reactive trivalent actiniae organometaiiic compounds. Derivatives of bis(pentamethylcyciopentadienyl)uranium(III)

Paul J. Pagan, Juan M. Manrsquez, Tobin J Marks, Cynthia S. Day, Sara H. Vollmer, Victor W. Day

Research output: Contribution to journalArticle

151 Citations (Scopus)

Abstract

Hydrogenolysis of the uranium(IV) alkyl complexes U[η5-(CH3)5C5]2(R)Cl results in clean reduction to the uranium(III) complex {U[η5-(CH3)5C5] 2(μ-Cl))3, which has been structurally characterized by single-crystal X-ray diffraction. This molecule crystallizes in the monoclinic space group C2/c - C2h6 (No. 15) with four molecules in a unit cell of dimensions a = 21.886 (7) Å, b = 14.236 (5) Å, c = 24.517 (7) Å, and β = 128.65 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.042 for 6813 independent reflections having 2θMoKα <65.2° and I > 3σ (I). The molecular structure consists of approximately D3h trimers with pseudotetrahedral U[η5-(CH3)5C5]2 units connected by bridging chloride ligands. The average U-C distance is 2.768 (11) Å, and the average U-Cl, 2.900 (2) Å. The average Cl-U-Cl angle is 83.8 (1)°. The trimer reacts with Lewis bases to form adducts U[η5-(CH3)5C5] 2Cl·L, where L = THF, pyridine, P(CH3)3, and (C2H5)2O. Stable, monomeric uranium(III) alkyl and amide complexes, U[η5-(CH3)5C5] 2CH[Si(CH3)3]2 and U[η5-(CH3)5C5] 2N[Si(CH3)3]2 can be prepared by the reaction of the chloride trimer with LiCH[Si(CH3)3]2 and NaN[Si(CH3)3]2, respectively. Reaction of unsaturated organic molecules with {U[η5-(CH3)5C5] 2(μ-Cl)}3 results in an interesting "disproportionation" reaction in which the trimer formally donates 1.5 equiv each of U[η5-(CH3)5C5]2 and U[η5-(CH3)5C5] 2Cl2. In particular, the reaction of diphenylacetylene, tetraphenylcyclopentadienone, and 9,10-phenanthrenequinone produces, respectively, [μ5-(CH3)5C5] 2UC(C6H5) = C(C6H5)C(C6H5) = C(C6H5), U[η5-(CH3)5C5] 22-COC4(C6H5) 4], and {U[η5(CH3)5C5] 2[9,10-phenanthrenequinonate]}x with an equivalent amount of U[η5-(CH3)5C5] 2Cl2 formed in each case. The reduction of U[η5-(CH3)5C5] 2Cl2 has been accomplished with sodium amalgam and, after workup, yields the complex U[η5-(CH3)5C5] 2Cl2Na·(THF)x. Sodium amalgam reduction of U[η5-(CH3)5C5] 2Cl2 in the presence of diphenylacetylene produces the uranotetraphenylcyclopentadiene complex in good yield. Overall, the organometallic chemistry of U(III) has distinct similarities to that of Ti(III), as well as to that of lanthanides in the +3 oxidation state.

Original languageEnglish
Pages (from-to)170-180
Number of pages11
JournalOrganometallics
Volume1
Issue number50
Publication statusPublished - 1982

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Actinium
actinium
Uranium
trimers
uranium
Mercury amalgams
Derivatives
mercury amalgams
Molecules
Chlorides
synthesis
Sodium
Lewis Bases
Lanthanoid Series Elements
Hydrogenolysis
chlorides
sodium
Organometallics
molecules
Amides

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis and properfies of a new class of highly reactive trivalent actiniae organometaiiic compounds. Derivatives of bis(pentamethylcyciopentadienyl)uranium(III). / Pagan, Paul J.; Manrsquez, Juan M.; Marks, Tobin J; Day, Cynthia S.; Vollmer, Sara H.; Day, Victor W.

In: Organometallics, Vol. 1, No. 50, 1982, p. 170-180.

Research output: Contribution to journalArticle

Pagan, Paul J. ; Manrsquez, Juan M. ; Marks, Tobin J ; Day, Cynthia S. ; Vollmer, Sara H. ; Day, Victor W. / Synthesis and properfies of a new class of highly reactive trivalent actiniae organometaiiic compounds. Derivatives of bis(pentamethylcyciopentadienyl)uranium(III). In: Organometallics. 1982 ; Vol. 1, No. 50. pp. 170-180.
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title = "Synthesis and properfies of a new class of highly reactive trivalent actiniae organometaiiic compounds. Derivatives of bis(pentamethylcyciopentadienyl)uranium(III)",
abstract = "Hydrogenolysis of the uranium(IV) alkyl complexes U[η5-(CH3)5C5]2(R)Cl results in clean reduction to the uranium(III) complex {U[η5-(CH3)5C5] 2(μ-Cl))3, which has been structurally characterized by single-crystal X-ray diffraction. This molecule crystallizes in the monoclinic space group C2/c - C2h6 (No. 15) with four molecules in a unit cell of dimensions a = 21.886 (7) {\AA}, b = 14.236 (5) {\AA}, c = 24.517 (7) {\AA}, and β = 128.65 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.042 for 6813 independent reflections having 2θMoKα <65.2° and I > 3σ (I). The molecular structure consists of approximately D3h trimers with pseudotetrahedral U[η5-(CH3)5C5]2 units connected by bridging chloride ligands. The average U-C distance is 2.768 (11) {\AA}, and the average U-Cl, 2.900 (2) {\AA}. The average Cl-U-Cl angle is 83.8 (1)°. The trimer reacts with Lewis bases to form adducts U[η5-(CH3)5C5] 2Cl·L, where L = THF, pyridine, P(CH3)3, and (C2H5)2O. Stable, monomeric uranium(III) alkyl and amide complexes, U[η5-(CH3)5C5] 2CH[Si(CH3)3]2 and U[η5-(CH3)5C5] 2N[Si(CH3)3]2 can be prepared by the reaction of the chloride trimer with LiCH[Si(CH3)3]2 and NaN[Si(CH3)3]2, respectively. Reaction of unsaturated organic molecules with {U[η5-(CH3)5C5] 2(μ-Cl)}3 results in an interesting {"}disproportionation{"} reaction in which the trimer formally donates 1.5 equiv each of U[η5-(CH3)5C5]2 and U[η5-(CH3)5C5] 2Cl2. In particular, the reaction of diphenylacetylene, tetraphenylcyclopentadienone, and 9,10-phenanthrenequinone produces, respectively, [μ5-(CH3)5C5] 2UC(C6H5) = C(C6H5)C(C6H5) = C(C6H5), U[η5-(CH3)5C5] 2[η2-COC4(C6H5) 4], and {U[η5(CH3)5C5] 2[9,10-phenanthrenequinonate]}x with an equivalent amount of U[η5-(CH3)5C5] 2Cl2 formed in each case. The reduction of U[η5-(CH3)5C5] 2Cl2 has been accomplished with sodium amalgam and, after workup, yields the complex U[η5-(CH3)5C5] 2Cl2Na·(THF)x. Sodium amalgam reduction of U[η5-(CH3)5C5] 2Cl2 in the presence of diphenylacetylene produces the uranotetraphenylcyclopentadiene complex in good yield. Overall, the organometallic chemistry of U(III) has distinct similarities to that of Ti(III), as well as to that of lanthanides in the +3 oxidation state.",
author = "Pagan, {Paul J.} and Manrsquez, {Juan M.} and Marks, {Tobin J} and Day, {Cynthia S.} and Vollmer, {Sara H.} and Day, {Victor W.}",
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TY - JOUR

T1 - Synthesis and properfies of a new class of highly reactive trivalent actiniae organometaiiic compounds. Derivatives of bis(pentamethylcyciopentadienyl)uranium(III)

AU - Pagan, Paul J.

AU - Manrsquez, Juan M.

AU - Marks, Tobin J

AU - Day, Cynthia S.

AU - Vollmer, Sara H.

AU - Day, Victor W.

PY - 1982

Y1 - 1982

N2 - Hydrogenolysis of the uranium(IV) alkyl complexes U[η5-(CH3)5C5]2(R)Cl results in clean reduction to the uranium(III) complex {U[η5-(CH3)5C5] 2(μ-Cl))3, which has been structurally characterized by single-crystal X-ray diffraction. This molecule crystallizes in the monoclinic space group C2/c - C2h6 (No. 15) with four molecules in a unit cell of dimensions a = 21.886 (7) Å, b = 14.236 (5) Å, c = 24.517 (7) Å, and β = 128.65 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.042 for 6813 independent reflections having 2θMoKα <65.2° and I > 3σ (I). The molecular structure consists of approximately D3h trimers with pseudotetrahedral U[η5-(CH3)5C5]2 units connected by bridging chloride ligands. The average U-C distance is 2.768 (11) Å, and the average U-Cl, 2.900 (2) Å. The average Cl-U-Cl angle is 83.8 (1)°. The trimer reacts with Lewis bases to form adducts U[η5-(CH3)5C5] 2Cl·L, where L = THF, pyridine, P(CH3)3, and (C2H5)2O. Stable, monomeric uranium(III) alkyl and amide complexes, U[η5-(CH3)5C5] 2CH[Si(CH3)3]2 and U[η5-(CH3)5C5] 2N[Si(CH3)3]2 can be prepared by the reaction of the chloride trimer with LiCH[Si(CH3)3]2 and NaN[Si(CH3)3]2, respectively. Reaction of unsaturated organic molecules with {U[η5-(CH3)5C5] 2(μ-Cl)}3 results in an interesting "disproportionation" reaction in which the trimer formally donates 1.5 equiv each of U[η5-(CH3)5C5]2 and U[η5-(CH3)5C5] 2Cl2. In particular, the reaction of diphenylacetylene, tetraphenylcyclopentadienone, and 9,10-phenanthrenequinone produces, respectively, [μ5-(CH3)5C5] 2UC(C6H5) = C(C6H5)C(C6H5) = C(C6H5), U[η5-(CH3)5C5] 2[η2-COC4(C6H5) 4], and {U[η5(CH3)5C5] 2[9,10-phenanthrenequinonate]}x with an equivalent amount of U[η5-(CH3)5C5] 2Cl2 formed in each case. The reduction of U[η5-(CH3)5C5] 2Cl2 has been accomplished with sodium amalgam and, after workup, yields the complex U[η5-(CH3)5C5] 2Cl2Na·(THF)x. Sodium amalgam reduction of U[η5-(CH3)5C5] 2Cl2 in the presence of diphenylacetylene produces the uranotetraphenylcyclopentadiene complex in good yield. Overall, the organometallic chemistry of U(III) has distinct similarities to that of Ti(III), as well as to that of lanthanides in the +3 oxidation state.

AB - Hydrogenolysis of the uranium(IV) alkyl complexes U[η5-(CH3)5C5]2(R)Cl results in clean reduction to the uranium(III) complex {U[η5-(CH3)5C5] 2(μ-Cl))3, which has been structurally characterized by single-crystal X-ray diffraction. This molecule crystallizes in the monoclinic space group C2/c - C2h6 (No. 15) with four molecules in a unit cell of dimensions a = 21.886 (7) Å, b = 14.236 (5) Å, c = 24.517 (7) Å, and β = 128.65 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.042 for 6813 independent reflections having 2θMoKα <65.2° and I > 3σ (I). The molecular structure consists of approximately D3h trimers with pseudotetrahedral U[η5-(CH3)5C5]2 units connected by bridging chloride ligands. The average U-C distance is 2.768 (11) Å, and the average U-Cl, 2.900 (2) Å. The average Cl-U-Cl angle is 83.8 (1)°. The trimer reacts with Lewis bases to form adducts U[η5-(CH3)5C5] 2Cl·L, where L = THF, pyridine, P(CH3)3, and (C2H5)2O. Stable, monomeric uranium(III) alkyl and amide complexes, U[η5-(CH3)5C5] 2CH[Si(CH3)3]2 and U[η5-(CH3)5C5] 2N[Si(CH3)3]2 can be prepared by the reaction of the chloride trimer with LiCH[Si(CH3)3]2 and NaN[Si(CH3)3]2, respectively. Reaction of unsaturated organic molecules with {U[η5-(CH3)5C5] 2(μ-Cl)}3 results in an interesting "disproportionation" reaction in which the trimer formally donates 1.5 equiv each of U[η5-(CH3)5C5]2 and U[η5-(CH3)5C5] 2Cl2. In particular, the reaction of diphenylacetylene, tetraphenylcyclopentadienone, and 9,10-phenanthrenequinone produces, respectively, [μ5-(CH3)5C5] 2UC(C6H5) = C(C6H5)C(C6H5) = C(C6H5), U[η5-(CH3)5C5] 2[η2-COC4(C6H5) 4], and {U[η5(CH3)5C5] 2[9,10-phenanthrenequinonate]}x with an equivalent amount of U[η5-(CH3)5C5] 2Cl2 formed in each case. The reduction of U[η5-(CH3)5C5] 2Cl2 has been accomplished with sodium amalgam and, after workup, yields the complex U[η5-(CH3)5C5] 2Cl2Na·(THF)x. Sodium amalgam reduction of U[η5-(CH3)5C5] 2Cl2 in the presence of diphenylacetylene produces the uranotetraphenylcyclopentadiene complex in good yield. Overall, the organometallic chemistry of U(III) has distinct similarities to that of Ti(III), as well as to that of lanthanides in the +3 oxidation state.

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