Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds

Paul J. Fagan, Juan M. Manriquez, Eric A. Maatta, Afif M. Seyam, Tobin J Marks

Research output: Contribution to journalArticle

378 Citations (Scopus)

Abstract

This paper reports the synthesis and chemical and physicochemical properties of thorium and uranium bis(pentamethylcyclopentadienyl) chlorides, hydrocarbyls, chlorohydrocarbyls, and hydrides. The reaction of the precursor compounds M[η5-(CH3)5C5] 2Cl2 with 2 equiv of lithium reagent RLi produces M[η5-(CH3)5C5]2R 2 compounds where R = CH3, CH2Si(CH3)3, CH2C(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) in good yield. With 1 equiv of lithium reagent, M[η5-(CH3)5C5]2(R)Cl compounds where R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) are formed in high yield. The M[η5-(CH3)5C5] 2(CH3)Cl compounds can be synthesized by redistribution between the corresponding dimethyl and dichloro complexes. The new organoactinides were thoroughly characterized by elemental analysis, 1H NMR and vibrational spectroscopy, and in many cases cryoscopic molecular weight measurements. The hydrocarbyls and chlorohydrocarbyls generally exhibit high thermal stability. However, the diphenyl compounds react readily with C6D6 to yield, via a benzyne complex, the corresponding M(C6D5)2 compounds. The thorium bis(neopentyl) complex reacts with benzene to produce the corresponding diphenyl complex. In probes of bond polarity, the dimethyl complexes react rapidly with acetone, alcohols, and iodine to produce respectively the corresponding terf-butoxides, alkoxides plus methane, and iodides plus methyl iodide. Competition experiments at -78 °C indicate that the thorium complexes are more reactive than those of uranium. The M[η5-(CH3)5C5]2R 2 compounds undergo hydrogenolysis to yield organoactinide hydrides, {M[η5-(CH3)5C5] 2(μ-H)H}2, and RH. While the thorium hydride exhibits high thermal stability, that of uranium readily (and reversibly) eliminates H2, forming a uranium(III) hydride. The new hydrides react vigorously with methyl chloride to produce methane and the corresponding chloro complexes, with acetone to produce isopropoxy complexes, and with alcohols to produce alkoxides and H2. The thorium chlorohydride, {Th[η5-(CH3)5C5] 2(μ-H)Cl}2, can be prepared by redistribution of the dichloride and dihydride; an alkoxyhydride, Th[η5-(CH3)5C5] 2[OC(CH3)3]H, can be prepared by hydrogenolysis of Th[η5-(CH3)5C5][OC(CH 3)3]CH3. In solution, the metal-bound hydrides of {Th[η5-(CH3)5C5] 2(μ-H)H}2 rapidly exchange with dissolved H2; this hydride also reacts with ethylene to yield the corresponding diethyl complex. The olefin addition and hydrogenolysis reactions can be coupled to effect homogeneous, catalytic olefin hydrogenation. The differences between thorium and uranium chemistry appear largely to reflect differences in accessible oxidation states and in metal-ligand bond polarity.

Original languageEnglish
Pages (from-to)6650-6667
Number of pages18
JournalJournal of the American Chemical Society
Volume103
Issue number22
Publication statusPublished - 1981

Fingerprint

Actinoid Series Elements
Organometallic Compounds
Thorium
Actinides
Organometallics
Uranium
Hydrides
Hydrogenolysis
Methane
Alkenes
Acetone
Lithium
Hydrogen
Olefins
Hot Temperature
Metals
Alcohols
Methyl Chloride
Thermodynamic stability
Hydrogenation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds. / Fagan, Paul J.; Manriquez, Juan M.; Maatta, Eric A.; Seyam, Afif M.; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 103, No. 22, 1981, p. 6650-6667.

Research output: Contribution to journalArticle

@article{eef3bc5b94644c12b1a7e9dbf019cd3e,
title = "Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds",
abstract = "This paper reports the synthesis and chemical and physicochemical properties of thorium and uranium bis(pentamethylcyclopentadienyl) chlorides, hydrocarbyls, chlorohydrocarbyls, and hydrides. The reaction of the precursor compounds M[η5-(CH3)5C5] 2Cl2 with 2 equiv of lithium reagent RLi produces M[η5-(CH3)5C5]2R 2 compounds where R = CH3, CH2Si(CH3)3, CH2C(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) in good yield. With 1 equiv of lithium reagent, M[η5-(CH3)5C5]2(R)Cl compounds where R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) are formed in high yield. The M[η5-(CH3)5C5] 2(CH3)Cl compounds can be synthesized by redistribution between the corresponding dimethyl and dichloro complexes. The new organoactinides were thoroughly characterized by elemental analysis, 1H NMR and vibrational spectroscopy, and in many cases cryoscopic molecular weight measurements. The hydrocarbyls and chlorohydrocarbyls generally exhibit high thermal stability. However, the diphenyl compounds react readily with C6D6 to yield, via a benzyne complex, the corresponding M(C6D5)2 compounds. The thorium bis(neopentyl) complex reacts with benzene to produce the corresponding diphenyl complex. In probes of bond polarity, the dimethyl complexes react rapidly with acetone, alcohols, and iodine to produce respectively the corresponding terf-butoxides, alkoxides plus methane, and iodides plus methyl iodide. Competition experiments at -78 °C indicate that the thorium complexes are more reactive than those of uranium. The M[η5-(CH3)5C5]2R 2 compounds undergo hydrogenolysis to yield organoactinide hydrides, {M[η5-(CH3)5C5] 2(μ-H)H}2, and RH. While the thorium hydride exhibits high thermal stability, that of uranium readily (and reversibly) eliminates H2, forming a uranium(III) hydride. The new hydrides react vigorously with methyl chloride to produce methane and the corresponding chloro complexes, with acetone to produce isopropoxy complexes, and with alcohols to produce alkoxides and H2. The thorium chlorohydride, {Th[η5-(CH3)5C5] 2(μ-H)Cl}2, can be prepared by redistribution of the dichloride and dihydride; an alkoxyhydride, Th[η5-(CH3)5C5] 2[OC(CH3)3]H, can be prepared by hydrogenolysis of Th[η5-(CH3)5C5][OC(CH 3)3]CH3. In solution, the metal-bound hydrides of {Th[η5-(CH3)5C5] 2(μ-H)H}2 rapidly exchange with dissolved H2; this hydride also reacts with ethylene to yield the corresponding diethyl complex. The olefin addition and hydrogenolysis reactions can be coupled to effect homogeneous, catalytic olefin hydrogenation. The differences between thorium and uranium chemistry appear largely to reflect differences in accessible oxidation states and in metal-ligand bond polarity.",
author = "Fagan, {Paul J.} and Manriquez, {Juan M.} and Maatta, {Eric A.} and Seyam, {Afif M.} and Marks, {Tobin J}",
year = "1981",
language = "English",
volume = "103",
pages = "6650--6667",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds

AU - Fagan, Paul J.

AU - Manriquez, Juan M.

AU - Maatta, Eric A.

AU - Seyam, Afif M.

AU - Marks, Tobin J

PY - 1981

Y1 - 1981

N2 - This paper reports the synthesis and chemical and physicochemical properties of thorium and uranium bis(pentamethylcyclopentadienyl) chlorides, hydrocarbyls, chlorohydrocarbyls, and hydrides. The reaction of the precursor compounds M[η5-(CH3)5C5] 2Cl2 with 2 equiv of lithium reagent RLi produces M[η5-(CH3)5C5]2R 2 compounds where R = CH3, CH2Si(CH3)3, CH2C(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) in good yield. With 1 equiv of lithium reagent, M[η5-(CH3)5C5]2(R)Cl compounds where R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) are formed in high yield. The M[η5-(CH3)5C5] 2(CH3)Cl compounds can be synthesized by redistribution between the corresponding dimethyl and dichloro complexes. The new organoactinides were thoroughly characterized by elemental analysis, 1H NMR and vibrational spectroscopy, and in many cases cryoscopic molecular weight measurements. The hydrocarbyls and chlorohydrocarbyls generally exhibit high thermal stability. However, the diphenyl compounds react readily with C6D6 to yield, via a benzyne complex, the corresponding M(C6D5)2 compounds. The thorium bis(neopentyl) complex reacts with benzene to produce the corresponding diphenyl complex. In probes of bond polarity, the dimethyl complexes react rapidly with acetone, alcohols, and iodine to produce respectively the corresponding terf-butoxides, alkoxides plus methane, and iodides plus methyl iodide. Competition experiments at -78 °C indicate that the thorium complexes are more reactive than those of uranium. The M[η5-(CH3)5C5]2R 2 compounds undergo hydrogenolysis to yield organoactinide hydrides, {M[η5-(CH3)5C5] 2(μ-H)H}2, and RH. While the thorium hydride exhibits high thermal stability, that of uranium readily (and reversibly) eliminates H2, forming a uranium(III) hydride. The new hydrides react vigorously with methyl chloride to produce methane and the corresponding chloro complexes, with acetone to produce isopropoxy complexes, and with alcohols to produce alkoxides and H2. The thorium chlorohydride, {Th[η5-(CH3)5C5] 2(μ-H)Cl}2, can be prepared by redistribution of the dichloride and dihydride; an alkoxyhydride, Th[η5-(CH3)5C5] 2[OC(CH3)3]H, can be prepared by hydrogenolysis of Th[η5-(CH3)5C5][OC(CH 3)3]CH3. In solution, the metal-bound hydrides of {Th[η5-(CH3)5C5] 2(μ-H)H}2 rapidly exchange with dissolved H2; this hydride also reacts with ethylene to yield the corresponding diethyl complex. The olefin addition and hydrogenolysis reactions can be coupled to effect homogeneous, catalytic olefin hydrogenation. The differences between thorium and uranium chemistry appear largely to reflect differences in accessible oxidation states and in metal-ligand bond polarity.

AB - This paper reports the synthesis and chemical and physicochemical properties of thorium and uranium bis(pentamethylcyclopentadienyl) chlorides, hydrocarbyls, chlorohydrocarbyls, and hydrides. The reaction of the precursor compounds M[η5-(CH3)5C5] 2Cl2 with 2 equiv of lithium reagent RLi produces M[η5-(CH3)5C5]2R 2 compounds where R = CH3, CH2Si(CH3)3, CH2C(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) in good yield. With 1 equiv of lithium reagent, M[η5-(CH3)5C5]2(R)Cl compounds where R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = Th) and R = CH2C(CH3)3, CH2Si(CH3)3, CH2C6H5, and C6H5 (M = U) are formed in high yield. The M[η5-(CH3)5C5] 2(CH3)Cl compounds can be synthesized by redistribution between the corresponding dimethyl and dichloro complexes. The new organoactinides were thoroughly characterized by elemental analysis, 1H NMR and vibrational spectroscopy, and in many cases cryoscopic molecular weight measurements. The hydrocarbyls and chlorohydrocarbyls generally exhibit high thermal stability. However, the diphenyl compounds react readily with C6D6 to yield, via a benzyne complex, the corresponding M(C6D5)2 compounds. The thorium bis(neopentyl) complex reacts with benzene to produce the corresponding diphenyl complex. In probes of bond polarity, the dimethyl complexes react rapidly with acetone, alcohols, and iodine to produce respectively the corresponding terf-butoxides, alkoxides plus methane, and iodides plus methyl iodide. Competition experiments at -78 °C indicate that the thorium complexes are more reactive than those of uranium. The M[η5-(CH3)5C5]2R 2 compounds undergo hydrogenolysis to yield organoactinide hydrides, {M[η5-(CH3)5C5] 2(μ-H)H}2, and RH. While the thorium hydride exhibits high thermal stability, that of uranium readily (and reversibly) eliminates H2, forming a uranium(III) hydride. The new hydrides react vigorously with methyl chloride to produce methane and the corresponding chloro complexes, with acetone to produce isopropoxy complexes, and with alcohols to produce alkoxides and H2. The thorium chlorohydride, {Th[η5-(CH3)5C5] 2(μ-H)Cl}2, can be prepared by redistribution of the dichloride and dihydride; an alkoxyhydride, Th[η5-(CH3)5C5] 2[OC(CH3)3]H, can be prepared by hydrogenolysis of Th[η5-(CH3)5C5][OC(CH 3)3]CH3. In solution, the metal-bound hydrides of {Th[η5-(CH3)5C5] 2(μ-H)H}2 rapidly exchange with dissolved H2; this hydride also reacts with ethylene to yield the corresponding diethyl complex. The olefin addition and hydrogenolysis reactions can be coupled to effect homogeneous, catalytic olefin hydrogenation. The differences between thorium and uranium chemistry appear largely to reflect differences in accessible oxidation states and in metal-ligand bond polarity.

UR - http://www.scopus.com/inward/record.url?scp=33845556470&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845556470&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:33845556470

VL - 103

SP - 6650

EP - 6667

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 22

ER -