Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS<sub>2</sub>

Lam, Oanh P.; Castro, Ludovic; Kosog, Boris; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

doi:10.1021/ic202535e

Cited by 55 publications

(57 citation statements)

References 16 publications

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“…The main position (55% occupancy) leads to aC ÀSd istance of 1.748 (15),t he minor position (45 %o ccupancy) leads to as horter CÀSd istance of 1.630 (16).T he CÀSd istances remain in the range of previously reported trithiocarbonate complexes. [26,27] There are two previous reports of trithiocarbonatec omplexes containing fe lements, [28,29] but the complex [Eu-(BPA)(CS 3 )(dmso) 2 ]i st he first example of at rithiocarbonate complex containing a4fe lement. Moreover, only three examples of CS 2 reduction by lanthanide complexes have been reported before.T he reduction of CS 2 by Eu 2 + and Yb 2 + tetrasiloxide complexes has been reported by our group [5c] and was found, by 13 CNMR studies, to afford trithiocarbonate and tetrathioxalate products in different ratios depending on the Ln 2 + ion.…”

Section: Reactivitymentioning

confidence: 99%

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Andrez

Bozoklu

Nocton

et al. 2015

Chemistry A European J

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The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O-donor tripodal ligands (tris(2-pyridylmethyl)amine (TPA), BPA(-) (HBPA=bis(2-pyridylmethyl)(2-hydroxybenzyl)amine), BPPA(-) (HBPPA=bis(2-pyridylmethyl)(3.5-di-tert-butyl-2-hydroxybenzyl)amine), and MPA(2-) (H2 MPA=(2-pyridylmethyl)bis(3.5-di-tert-butyl-2-hydroxybenzyl)amine) is reported. The X-ray crystal structures of the heteroleptic Ln(2+) complexes [Ln(TPA)I2 ] (Ln=Eu, Yb) and [Yb(BPA)I(CH3 CN)]2 , of the Ln(2+) homoleptic [Ln(TPA)2 ]I2 (Ln=Sm, Eu, Yb) and [Eu(BPA)2 ] complexes, and of the Ln(3+) [Eu(BPPA)2 ]OTf and [Yb(MPA)2 K(dme)2 ] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis-ligand complexes of Eu(3+) and Yb(3+) show that the metal center reduction occurs at significantly lower potentials for the BPA(-) ligand as compared with the TPA ligand. This suggests that the more electron-rich character of the BPA(-) ligand results in a higher reducing character of the lanthanide complexes of BPA(-) compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis-TPA complexes of Eu(2+) and Yb(2+) do not show any reactivity with heteroallenes, the [Eu(BPA)2 ] complex reduces CS2 to afford the first example of a lanthanide trithiocarbonate complex.

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Section: Reactivitymentioning

confidence: 99%

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Andrez

Bozoklu

Nocton

et al. 2015

Chemistry A European J

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“…This is in line with previous reports on CS 2 activation with either Sm II or U III complexes, where the low kinetic stability of the formed CS was already underlined. [29][30][31] In the same way, on the basis of previous work, [29] the formation of thiooxalate is predicted to involve a relatively high barrier preventing this reactivity. Finally, the C-S bond formation was investigated.…”

Section: Resultsmentioning

confidence: 65%

“…This C-S bond formation is reminiscent of the C-O bond formation reported by Castro et al in carbonate formation in U III and Sm II chemistry. [30][31][32][33] How-ever, in the latter, after C-O bond formation, C-O bond cleavage occurred to form a CO molecule. Interestingly, in this study (Figure 3), C-S bond breaking is not observed, which strengthens the argument of the lack of stability of the CS molecule.…”

Section: Resultsmentioning

confidence: 99%

Activation of Heteroallenes CO_xS_2–x (x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato Sm^II Complex

et al. 2016

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A joint experimental/theoretical (DFT) study of the activation of heteroallenes CO x S 2-x (x = 0-2) by [Sm(Giso) 2 ] {Giso -= [(ArN) 2 CNCy 2 ] -, Cy = cyclohexyl, Ar = 2,6-diisopropylphenyl} is reported. All heteroallenes are reduced in a different manner. Indeed, while activation of CS 2 yields a bimetallic CS 2 coupled product through C-S bond formation, CO 2 forms an oxalate complex through C-C bond formation. This subsequently undergoes CO 2 insertion into one of its Sm-N bonds. Finally, COS activation is predicted to yield a dithio-

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“…The insertion of CS 2 into U–element bonds is exceedingly rare,7, 12 and only one example has been reported for UC bonds, involving the U 3+ alkyl complex [Tp* 2 U(CH 2 Ph)], which yields 10 7a. Complex 6 is therefore the first example of the insertion of CS 2 into a U 4+ alkyl bond.…”

Section: Discussionmentioning

confidence: 99%

Synthesis and Insertion Chemistry of Mixed Tether Uranium Metallocene Complexes

Siladke

Leduc

Evans

2012

Chemistry A European J

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The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2)U] (1) with substrates that react with only one of the U-C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U-C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN(3)) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U(η(5)-C(5)Me(4)SiMe(2)-CH(2)NNN-Ad-κ(2)N(1,3))]. Similarly, a single equivalent of CS(2) reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U(η(5)-C(5)Me(4)SiMe(2)-CH(2)C(S)(2)-κ(2)S,S')], a reaction that constitutes the first example of CS(2) insertion into a U(4+)-C bond. Complex 1 reacts with one equivalent of pyridine N-oxide by C-H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N-oxide complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(η(5)-C(5)Me(4)SiMe(3))U(C(6)H(4)NO-κ(2)C,O)]. The remaining (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2-) ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η(5)-C(5)Me(4)SiMe(3))U(C(5)H(4)NO-κ(2)C,O)(η(5)-C(5)Me(4)SiMe(2)C(=CH(2))O-κO)] and [(η(5)-C(5)Me(4)SiMe(2)CH(2)NNN-Ad-κ(2)N(1,3))U(η(5)-C(5)Me(4)SiMe(2)C(=CH(2))O-κO)].

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Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS₂

Cited by 55 publications

References 16 publications

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Activation of Heteroallenes CO_xS_2–x (x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato Sm^II Complex

Synthesis and Insertion Chemistry of Mixed Tether Uranium Metallocene Complexes

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Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS2

Cited by 55 publications

References 16 publications

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

Activation of Heteroallenes COxS2–x (x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato SmII Complex

Synthesis and Insertion Chemistry of Mixed Tether Uranium Metallocene Complexes

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Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS₂

Activation of Heteroallenes CO_xS_2–x (x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato Sm^II Complex