Carbene Complexes of Neptunium

Conrad A. P. Goodwin; Ashley J. Wooles; Jesse Murillo; Erli Lu; Josef T. Boronski; Brian L. Scott; Andrew J. Gaunt; Stephen T. Liddle

doi:10.1021/jacs.2c02152

Carbene Complexes of Neptunium

Conrad A. P. Goodwin
, Ashley J. Wooles
, Jesse Murillo
, Erli Lu
, Josef T. Boronski
, Brian L. Scott
, Andrew J. Gaunt^*
, Stephen T. Liddle^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N-heterocyclic carbene–neptunium(III) complexes that exhibit polarized-covalent σ²π² multiple and dative σ² single transuranium-carbon bond interactions, respectively. The reaction of [Np^IIII₃(THF)₄] with [Rb(BIPM^TMSH)] (BIPM^TMSH = {HC(PPh₂NSiMe₃)₂}^1–) affords [(BIPM^TMSH)Np^III(I)₂(THF)] (3Np) in situ, and subsequent treatment with the N-heterocyclic carbene {C(NMeCMe)₂} (I^Me4) allows isolation of [(BIPM^TMSH)Np^III(I)₂₍I^Me4)] (4Np). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPM^TMS)Np^III(I)(DME)] (5Np, BIPM^TMS = {C(PPh₂NSiMe₃)₂}^2–). Analogously, addition of benzyl potassium and I^Me4 to 4Np gives [(BIPM^TMS)Np^III(I)(I^Me4)₂] (6Np). The synthesis of 3Np–6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np–6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these Np^III═C bonds are more covalent than U^III═C, Ce^III═C, and Pm^III═C congeners but comparable to analogous U^IV═C bonds in terms of bond orders and total metal contributions to the M═C bonds. A preliminary assessment of Np^III═C reactivity has introduced multiple bond metathesis to transuranium chemistry, extending the range of known metallo-Wittig reactions to encompass actinide oxidation states III-VI.

Original language	English
Pages (from-to)	9764-9774
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	144
Issue number	22
Early online date	24 May 2022
DOIs	https://doi.org/10.1021/jacs.2c02152
Publication status	Published - 8 Jun 2022

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@article{576914f9bd2242a397146736a55a10af,

title = "Carbene Complexes of Neptunium",

abstract = "Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N-heterocyclic carbene–neptunium(III) complexes that exhibit polarized-covalent σ2π2 multiple and dative σ2 single transuranium-carbon bond interactions, respectively. The reaction of [NpIIII3(THF)4] with [Rb(BIPMTMSH)] (BIPMTMSH = \{HC(PPh2NSiMe3)2\}1–) affords [(BIPMTMSH)NpIII(I)2(THF)] (3Np) in situ, and subsequent treatment with the N-heterocyclic carbene \{C(NMeCMe)2\} (IMe4) allows isolation of [(BIPMTMSH)NpIII(I)2(IMe4)] (4Np). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPMTMS)NpIII(I)(DME)] (5Np, BIPMTMS = \{C(PPh2NSiMe3)2\}2–). Analogously, addition of benzyl potassium and IMe4 to 4Np gives [(BIPMTMS)NpIII(I)(IMe4)2] (6Np). The synthesis of 3Np–6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np–6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these NpIII═C bonds are more covalent than UIII═C, CeIII═C, and PmIII═C congeners but comparable to analogous UIV═C bonds in terms of bond orders and total metal contributions to the M═C bonds. A preliminary assessment of NpIII═C reactivity has introduced multiple bond metathesis to transuranium chemistry, extending the range of known metallo-Wittig reactions to encompass actinide oxidation states III-VI.",

author = "Goodwin, \{Conrad A. P.\} and Wooles, \{Ashley J.\} and Jesse Murillo and Erli Lu and Boronski, \{Josef T.\} and Scott, \{Brian L.\} and Gaunt, \{Andrew J.\} and Liddle, \{Stephen T.\}",

year = "2022",

month = jun,

day = "8",

doi = "10.1021/jacs.2c02152",

language = "English",

volume = "144",

pages = "9764--9774",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Carbene Complexes of Neptunium

AU - Goodwin, Conrad A. P.

AU - Wooles, Ashley J.

AU - Murillo, Jesse

AU - Lu, Erli

AU - Boronski, Josef T.

AU - Scott, Brian L.

AU - Gaunt, Andrew J.

AU - Liddle, Stephen T.

PY - 2022/6/8

Y1 - 2022/6/8

N2 - Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N-heterocyclic carbene–neptunium(III) complexes that exhibit polarized-covalent σ2π2 multiple and dative σ2 single transuranium-carbon bond interactions, respectively. The reaction of [NpIIII3(THF)4] with [Rb(BIPMTMSH)] (BIPMTMSH = {HC(PPh2NSiMe3)2}1–) affords [(BIPMTMSH)NpIII(I)2(THF)] (3Np) in situ, and subsequent treatment with the N-heterocyclic carbene {C(NMeCMe)2} (IMe4) allows isolation of [(BIPMTMSH)NpIII(I)2(IMe4)] (4Np). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPMTMS)NpIII(I)(DME)] (5Np, BIPMTMS = {C(PPh2NSiMe3)2}2–). Analogously, addition of benzyl potassium and IMe4 to 4Np gives [(BIPMTMS)NpIII(I)(IMe4)2] (6Np). The synthesis of 3Np–6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np–6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these NpIII═C bonds are more covalent than UIII═C, CeIII═C, and PmIII═C congeners but comparable to analogous UIV═C bonds in terms of bond orders and total metal contributions to the M═C bonds. A preliminary assessment of NpIII═C reactivity has introduced multiple bond metathesis to transuranium chemistry, extending the range of known metallo-Wittig reactions to encompass actinide oxidation states III-VI.

AB - Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N-heterocyclic carbene–neptunium(III) complexes that exhibit polarized-covalent σ2π2 multiple and dative σ2 single transuranium-carbon bond interactions, respectively. The reaction of [NpIIII3(THF)4] with [Rb(BIPMTMSH)] (BIPMTMSH = {HC(PPh2NSiMe3)2}1–) affords [(BIPMTMSH)NpIII(I)2(THF)] (3Np) in situ, and subsequent treatment with the N-heterocyclic carbene {C(NMeCMe)2} (IMe4) allows isolation of [(BIPMTMSH)NpIII(I)2(IMe4)] (4Np). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPMTMS)NpIII(I)(DME)] (5Np, BIPMTMS = {C(PPh2NSiMe3)2}2–). Analogously, addition of benzyl potassium and IMe4 to 4Np gives [(BIPMTMS)NpIII(I)(IMe4)2] (6Np). The synthesis of 3Np–6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np–6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these NpIII═C bonds are more covalent than UIII═C, CeIII═C, and PmIII═C congeners but comparable to analogous UIV═C bonds in terms of bond orders and total metal contributions to the M═C bonds. A preliminary assessment of NpIII═C reactivity has introduced multiple bond metathesis to transuranium chemistry, extending the range of known metallo-Wittig reactions to encompass actinide oxidation states III-VI.

U2 - 10.1021/jacs.2c02152

DO - 10.1021/jacs.2c02152

M3 - Article

SN - 0002-7863

VL - 144

SP - 9764

EP - 9774

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 22

ER -

Carbene Complexes of Neptunium

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