Formation of Methane versus Benzene in the Reactions of (C5Me5)2Th(CH3)2 with [CH3PPh3]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

Rungthanaphatsophon, Pokpong; Bathelier, Adrien; Castro, Ludovic; Behrle, Andrew C.; Barnes, Charles L.; Maron, Laurent; Walensky, Justin R.

doi:10.1002/ange.201706496

Cited by 10 publications

(7 citation statements)

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“…Walensky et al followed route C to obtain uranium and thorium complexes featuring triphenylphosphinomethylene ligand 73. 217,218 Starting from [Cp* 2 Th(Me) 2 ], a competitive methylene-phenyl exchange at phosphorus was observed as a side reaction (Scheme 106). 217 to be the shortest reported to date (2.2428(2) Å, X = Cl; 2.252(4) Å, X = Br; 2.2454(2) Å, X = I).…”

Section: Coordination Chemistry Of Type II Geminal Dianionsmentioning

confidence: 99%

“…217,218 Starting from [Cp* 2 Th(Me) 2 ], a competitive methylene-phenyl exchange at phosphorus was observed as a side reaction (Scheme 106). 217 to be the shortest reported to date (2.2428(2) Å, X = Cl; 2.252(4) Å, X = Br; 2.2454(2) Å, X = I). In the case of thorium complexes, it was deduced from 13 C NMR data that the Th−C bond had more π bond character than the thorium complex featuring a methanediide ligand (vide supra).…”

Section: Coordination Chemistry Of Type II Geminal Dianionsmentioning

confidence: 99%

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Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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Section: Coordination Chemistry Of Type II Geminal Dianionsmentioning

confidence: 99%

Section: Coordination Chemistry Of Type II Geminal Dianionsmentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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“…Actinide–ligand multiple bonds can elucidate the role of the valence orbitals in the structure, bonding, and reactivity of the actinides . While first synthesized more than 40 years ago, few actinide–carbon multiple bonds have been reported, − and most involve the tetravalent oxidation state. All actinide–carbenoid complexes have an An–C bond that is stabilized by a heteroatom, − typically phosphorus, yielding phosphorano-stabilized carbenes or methandiides. , Only recently has the Hayton group used an allenylidene ligand to produce short An–C multiple bonds, but the major resonance form was primarily of An–C single-bond character .…”

Section: Introductionmentioning

confidence: 99%

“…The structure of 1 is as expected with a short U−N bond distance of 1.989(9) Å and a U−I bond distance of 3.0443(7) Å, which are nearly identical to those found in Kiplinger's analogous iodide structures, [(C 5 Me 5 ) 2 U(I)(�NAr)] [for Ar = 2,6-i Pr 2 C 6 H 3 , U−N, 1.974(7) Å, and U−I, 3.0385(7) Å; for Ar = 2,6-t Bu 2 C 6 H 3 , U−N, 1.975(6) Å, and U−I, 3.0116(6) Å]. 19 All of the U(V) imido halide complexes of Kiplinger and co-workers have U� N−C(ipso) bond angles of 169.6(4)−172.2(9)°, 19,20 while a nearly linear angle of 178.4 (7)°was found in 1.…”

Section: ■ Introductionmentioning

confidence: 99%

Structure of Uranium(V) Methyl and Uranium(IV) Ylide Complexes

Rungthanaphatsophon,

Stanistreet-Welsh,

Ward

et al. 2023

Organometallics

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Syntheses of rare examples of U(V) methyl and U(IV) ylide complexes are reported. Reaction of the previously reported U(IV) imido complex [(C 5 Me 5 ) 2 U(py)(�NMes)] (py = pyridine, and Mes = 2,4,6-Me 3 C 6 H 2 ) with CuI forms the U(V) complex [(C 5 Me 5 ) 2 U(I)(�NMes)]. Reaction of the iodo complex with MgMe 2 produces the methyl complex [(C 5 Me 5 ) 2 U-(CH 3 )(�NMes)]. The methyl complex was reacted with CH 2 PPh 3 , surprisingly forming [(C 5 Me 5 ) 2 U(CH 2 PPh 3 )(�NMes)], a U(IV) ylide. This is formed from a disproportionation of a transient U(V) carbene, leading to the U(IV) ylide and a U(VI) bis(imido) complex, [(C 5 Me 5 ) 2 U(�NMes) 2]. These complexes were characterized using spectroscopic methods (nuclear magnetic resonance, infrared, and ultraviolet−visible−nean infrared), SQUID magnetometry, and X-ray crystallography, and density functional theory calculations are used to compare the U(V) methyl with the targeted U(V) carbene ligands.

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“…[83][84] While no alkylidene complexes are known with the f elements, terminal phosphorano-stabilized carbene complexes were first realized by Gilje and Kramer in 1981, and have become increasingly used due to their tendency to form short metal-carbon bonds. 15,[26][27][85][86] Shorter bond distances are due to the resonance between an alkyl and metalated ylide forms of the ligand, eq 1.…”

Section: Thorium(iv) and Uranium(iv)-carbon Bonds Introductionmentioning

confidence: 99%

Synthesis and reactivity of actinide phosphorano-stabilized carbene and phosphido complexes

Rungthanaphatsophon¹

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Nuclear power plants have been operated in the United States for over 60 years, generating over 800 terawatt-hours of energy per year. However, there is still no reliable process to recycle the spent nuclear fuel. This dissertation looks at the formation of actinide-ligand multiple bonds, which may give us insights into how to improve the process of separation of actinides from the spent nuclear fuels contaminated with lanthanides. This is because lanthanides cannot participate in multiple bonding and a difference in coordination chemistry between actinides and lanthanides is important in separation methods. This dissertation contains two parts, both of which involve using phosphorus to create new actinide complexes. Chapters 1 and 2 outline the use of phosphorano-stabilized carbene complexes to make short actinide-carbon bonds. In fact, these complexes exhibit the shortest uranium and thorium-carbon bonds reported in the literature. Chapter 3 revolves around investigating the synthesis, characterization, and reactivity of actinide phosphido (monoanionic phosphine) complexes. In this regard, I have synthesized the first trivalent uranium phosphido complex, (C5Me5)2U[P(SiMe3)(2,4,6- Me3C6H2)](THF). The investigation of its reactivity revealed that the complex is capable of 4-electron reduction chemistry. For example, the reaction of (C5Me5)2U[P(SiMe3)(2,4,6-Me3C6H2)](THF) with azidotrimethylsilane, N3SiMe3, produces a U(VI) complex. Three electrons are from the metal center, U(III) to U(VI), and one electron is from reductive coupling of the phosphido ligand. The phosphido chemistry can also be extended to tetravalent uranium and thorium. Chapter 4 outlines the synthesis of thorium phosphido complexes which exhibit an unusual absorption in the visible region which we contributed to a ligand to metal charge transfer. Just by varying the ligand design, we were able to manipulate the HOMO/LUMO gap, which results in an absorption in a different part of the visible region. Appendix A summaries the synthesis of copper(I) complexes with bulky terphenyl ligands. The steric properties of the complex center can be tuned by changing the substituent on the terphenyl. By carefully controlling the steric properties, different coordinating environments around the metal center can be achieved. Finally, Appendix B describes the reactivity of U(IV) phosphido complexes with organic azide and tert-butyl isocyanide.

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Formation of Methane versus Benzene in the Reactions of (C₅Me₅)₂Th(CH₃)₂ with [CH₃PPh₃]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

Cited by 10 publications

References 42 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Structure of Uranium(V) Methyl and Uranium(IV) Ylide Complexes

Synthesis and reactivity of actinide phosphorano-stabilized carbene and phosphido complexes

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