Organoactinide-catalyzed oligomerization of terminal acetylenes

Straub, Thomas; Haskel, Ariel; Eisen, Moris S.

doi:10.1021/ja00128a029

Cited by 87 publications

(60 citation statements)

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“…The same regioselective insertion of TMSCMCH to an organothorium alkenyl complex was observed in organoactinide-catalyzed oligomerization of alkynes. 88,89 ð20Þ ð21Þ…”

Section: Catalytic Hydrosilylation Of Terminal Alkynes Catalytic Hydr...mentioning

confidence: 99%

Recent advances in organothorium and organouranium catalysis

2008

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In this critical review we summarize the latest results obtained during the last decade concerning the catalytic activities of organoactinide complexes. We begin with a brief summary of the synthesis and characterization of uranium and thorium complexes that later will be used as catalysts for demanding chemical transformations. Hydroamination, hydrosilylation of terminal alkynes, coupling of terminal alkynes with isonitriles, catalytic reduction of azides and hydrazines, ring opening polymerization of cyclic esters and polymerization of alpha-olefins are covered in this review (118 references). The topics covered in this review regarding organoactinide chemistry will be of interest to inorganic, organic and organometallic chemists, material and catalytic scientists due to its unique mode of activation as compared to late transition-metals. In addition, the field of organoactinide complexes in catalysis is steadily growing, because of the complementary reactivity of organoactinides as compared to other early or late transition complexes, in demanding chemical transformations.

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“…The same regioselective insertion of TMSCMCH to an organothorium alkenyl complex was observed in organoactinide-catalyzed oligomerization of alkynes. 88,89 ð20Þ ð21Þ…”

Section: Catalytic Hydrosilylation Of Terminal Alkynes Catalytic Hydr...mentioning

confidence: 99%

Recent advances in organothorium and organouranium catalysis

2008

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“…Compared to the hundreds of reported transition metal and lanthanide hydrides, there are only a limited number of thorium and uranium hydride complexes. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] The bis(pentamethylcyclopentadienyl) complexes [(C 5 Me 5 ) 2 An(H)(m-H)] 2 (An = Th (1), U (2)) were the first isolable organoactinide hydride complexes; 12 and since their introduction in 1982, they have displayed a palette of chemical reactivity such as the stoichiometric and catalytic hydrogenation of unsaturated substrates, 9,12,[15][16][17] the catalytic dimerization of propylene, 18,19 coupling reactions, [20][21][22] and multi-electron reductions (following liberation of H 2 ). 13,14,[23][24][25] The chemistry of actinide hydrides is still not well understood.…”

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confidence: 99%

Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides

et al. 2015

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The thorium and uranium dihydride dimer complexes [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) have been easily prepared using phenylsilane, which is an efficient and safer alternative to hydrogen gas. The synthetic utility of this new hydriding method has been demonstrated by the preparation of a variety of organometallic complexes, including, for the first time, (C5Me5)2U(SMe)2, (C5Me5)2Th(C4Ph4), (C5Me5)2U(C4Ph4), (C5Me5)2ThS5, and (C5Me5)2U(bipy) using [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) as multi-electron reductants.

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“…Uranium(IV) complexes have also been documented for the oligomerization of alkynes, as early as 1995, when [(Cp*) 2 U(Me) 2 ] ( 5 ) was found to catalyze the synthesis of alkyne trimers and dimers. 32 It was found that, under catalytic conditions, reactions with tert -butyl-substituted alkynes resulted in oligomerization to form (noncyclic) trimers through path B ( Figure 8 A, red), while TMS- or phenyl-substituted alkynes preferred linear dimers through path A ( Figure 6 A, black). In 2015, Eisen et al demonstrated that changing from [(Cp*) 2 U(Me) 2 ] ( 5 ) to [(Me 3 Si) 2 U(κ 2 -(N,C)–CH 2 Si(CH 3 ) 2 -N(SiMe 3 )] ( 8 ) allowed for cyclotrimerization to occur ( Figure 4 A, blue), which results in a statistical mixture of 1,2,4- and 1,3,5-arenes ( Figure 8 B) in the cases of phenyl acetylene and tert- butyl acetylene.…”

Section: Oligomerizationmentioning

confidence: 99%

From Chemical Curiosities and Trophy Molecules to Uranium-Based Catalysis: Developments for Uranium Catalysis as a New Facet in Molecular Uranium Chemistry

Hartline

Meyer

2021

JACS Au

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Catalysis remains one of the final frontiers in molecular uranium chemistry. Depleted uranium is mildly radioactive, continuously generated in large quantities from the production and consumption of nuclear fuels and accessible through the regeneration of “uranium waste”. Organometallic complexes of uranium possess a number of properties that are appealing for applications in homogeneous catalysis. Uranium exists in a wide range of oxidation states, and its large ionic radii support chelating ligands with high coordination numbers resulting in increased complex stability. Its position within the actinide series allows it to involve its f -orbitals in partial covalent bonding; yet, the U–L bonds remain highly polarized. This causes these bonds to be reactive and, with few exceptions, relatively weak, allowing for high substrate on/off rates. Thus, it is reasonable that uranium could be considered as a source of metal catalysts. Accordingly, uranium complexes in oxidation states +4, +5, and +6 have been studied extensively as catalysts in sigma-bond metathesis reactions, with a body of literature spanning the past 40 years. High-valent species have been documented to perform a wide variety of reactions, including oligomerization, hydrogenation, and hydrosilylation. Concurrently, electron-rich uranium complexes in oxidation states +2 and +3 have been proven capable of performing reductive small molecule activation of N 2 , CO 2 , CO, and H 2 O. Hence, uranium’s ability to activate small molecules of biological and industrial relevance is particularly pertinent when looking toward a sustainable future, especially due to its promising ability to generate ammonia, molecular hydrogen, and liquid hydrocarbons, though the advance of catalysis in these areas is in the early stages of development. In this Perspective, we will look at the challenges associated with the advance of new uranium catalysts, the tools produced to combat these challenges, the triumphs in achieving uranium catalysis, and our future outlook on the topic.

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Organoactinide-catalyzed oligomerization of terminal acetylenes

Abstract: Various actinide alkyl and hydride metallocenes effectively and selectively catalyze a variety of C-H bond activation and hydrogenation reactions.1 In their "cationic" form, these d°/f°m etallocene complexes have recently been shown to be very

Cited by 87 publications

References 0 publications

Recent advances in organothorium and organouranium catalysis

Recent advances in organothorium and organouranium catalysis

Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides

From Chemical Curiosities and Trophy Molecules to Uranium-Based Catalysis: Developments for Uranium Catalysis as a New Facet in Molecular Uranium Chemistry

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