Formation of a Uranium-Bound η1-Cyaphide (CP–) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP–)

Hoerger, Christopher J.; Heinemann, Frank W.; Louyriac, Elisa; Maron, Laurent; Grützmacher, Hansjörg; Meyer, Karsten

doi:10.1021/acs.organomet.7b00590

Cited by 70 publications

(82 citation statements)

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“…Thesalient feature of this structure is that ah ighly-bent P-C-O moiety resides between two [U-(Tren TIPS )] units in the anion component. [6,9] TheP ÀCd istance is elongated in 3 by almost 0.2 compared to 2 and other U-OCP linkages; [6,9] indeed, Scheme 1. [6,9] TheP ÀCd istance is elongated in 3 by almost 0.2 compared to 2 and other U-OCP linkages; [6,9] indeed, Scheme 1.…”

Section: Angewandte Chemiementioning

confidence: 88%

“…[12] Noting the prior incompatibility of uranium(III) with OCP À , [6] but that less reducing uranium(IV) congeners afford isolable OCP À derivatives, [6,9] we first sought to introduce the OCP À anion to au ranium(IV)-Tren TIPS fragment. [12] Noting the prior incompatibility of uranium(III) with OCP À , [6] but that less reducing uranium(IV) congeners afford isolable OCP À derivatives, [6,9] we first sought to introduce the OCP À anion to au ranium(IV)-Tren TIPS fragment.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[1] Although the oxidation chemistry of the OCP À anion is now quite established, [1] reports of its formal reduction chemistry are exceedingly scarce. Forexample,strongly reducing [U{N(OAr Ad,Me ) 3 }(DME)] [N(OAr Ad,Me ) 3 = trianion of tris(2hydroxy-3-(1-adamantyl)-5-methylbenzyl)amine] cleaves the CÀObond of OCP À to give an oxo-bridged dinuclear product containing cyaphide,CP À , [6] whereas the more weakly reducing [Ti(OCP){HC(CMeNAr) 2 }(OAr)] (Ar = 2,6-diisopropylphenyl) cleaves the C À Pb ond to release CO and give aP 2 derivative. Forexample,strongly reducing [U{N(OAr Ad,Me ) 3 }(DME)] [N(OAr Ad,Me ) 3 = trianion of tris(2hydroxy-3-(1-adamantyl)-5-methylbenzyl)amine] cleaves the CÀObond of OCP À to give an oxo-bridged dinuclear product containing cyaphide,CP À , [6] whereas the more weakly reducing [Ti(OCP){HC(CMeNAr) 2 }(OAr)] (Ar = 2,6-diisopropylphenyl) cleaves the C À Pb ond to release CO and give aP 2 derivative.…”

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Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

Magnall

Baláȥs

et al. 2019

Angewandte Chemie

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Section: Angewandte Chemiementioning

confidence: 88%

Section: Angewandte Chemiementioning

confidence: 99%

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confidence: 99%

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Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

Magnall

Baláȥs

et al. 2019

Angewandte Chemie

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“…Such bent coordination modes are common to all of the known phosphaketenyl compounds isolated, and can in fact be related to the bent geometry observed for the parent acid OCPH. [35] The bonding in these phosphaethynolato species has much greater ionic character than in phosphaketenyl-type compounds,and results in as ignificant shortening of the P À Cb onds and ac oncomitant lengthening of the C À Ob onds of the anion relative to those observed for phosphorus-bonded species. This bonding mode was first structurally authenticated in the coordination sphere of the actinide elements in (amid) 3 M(OCP) (C;M= U, Th ;w here amid = N,N'-bis-(trimethylsilyl)benzamidinate; Figure 2).…”

Section: Coordination Chemistry and Salt Metathesismentioning

confidence: 99%

“…This bonding mode was first structurally authenticated in the coordination sphere of the actinide elements in (amid) 3 M(OCP) (C;M= U, Th ;w here amid = N,N'-bis-(trimethylsilyl)benzamidinate; Figure 2). [35] Coordination of the OCP À anion to am etal centre via the oxygen atom also permits for the reductive dimerization of two OCP À units to afford the formally tetra-anionic [OCPPCO] 4À ligand, which has recently been achieved from the reduction of the scandium complex {CH[N(Dipp)C(CH 3 )] 2 }Sc(ODipp)(THF)(OCP) (D;F igure 2). [35] The bonding in these phosphaethynolato species has much greater ionic character than in phosphaketenyl-type compounds,and results in as ignificant shortening of the P À Cb onds and ac oncomitant lengthening of the C À Ob onds of the anion relative to those observed for phosphorus-bonded species.…”

Section: Coordination Chemistry and Salt Metathesismentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO]⁴⁻

et al. 2017

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The first example of the OCPPCO ligand, diisophosphaethynolate,isreported via reductive coupling of aSc À OCP precursor.U pon reduction with KC 8 ,i solation of the dinuclear complex, namely [K(OEt 2 )] 2 [(nacnac)Sc(OAr)] 2 -(OCPPCO), is observed, leading to au nique motif [OCPPCO] 4À ,s tabilized by two scandium centers.D etailed NMR spectra of all complexes as well as IR and single crystal X-ray studies were obtained to fully elucidate the nature of these complexes in solution as well as in the solid state.Theory is combined to probe the electronic structure and orbitals responsible for the bonding interactions in the ScÀOCPPCOÀ Sc skeleton but also to compare to the linear mode observed in the precursor.Diisooxocyan, OCN À NCO,isahighly unstable species that can be generated via oxidation of ubiquitous [NCO] À . [1] We inquired whether the analogous OCPÀPCO,d iisophosphaethynolate,c ould be stabilized with early transition metals, especially under reducing conditions,g iven the more likely ability of phosphorous to catenate.Since the recent report of the facile synthesis of the phosphaethynolate ion, Na(OCP)(dioxane) 2.5 , [2] the accessibility of this reagent has prompted its use for chemistry on both transition-metal scaffolds as well as in organic transformations. [3] Va rious studies with transition metal and actinide complexes has revealed the ambidentate nature of the À OCP ion, that is, binding via its Oo rPatom depending on the metal in question and supporting ligand scaffold as well as the respective oxidation state of the metal. [3, 4] Recently,w er eported the reactivity of the phosphaethynolate ion with the d 1 species (nacnac)TiCl(OAr) (nacnac À = [ArNC(CH 3 )] 2 CH;A r = 2,6-i Pr 2 C 6 H 3 ), which furnished an early planar Ti 2 P 2 core in [(nacnac)Ti(OAr)] 2 (m 2 :h 2 ,h 2 -P 2 ) by decarbonylation and P À Pr adical coupling steps. [5] In considering the observed reactivity in the Ti III system, and also the known reactivity of early-transition-metal isocyanate complexes to undergo decarbonylation to form nitride anions, [6] we sought to determine if the À OCP reagent could

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Formation of a Uranium-Bound η¹-Cyaphide (CP^–) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP^–)

Cited by 70 publications

References 46 publications

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

The Chemistry of the 2‐Phosphaethynolate Anion

A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO]⁴⁻

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Formation of a Uranium-Bound η1-Cyaphide (CP–) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP–)

Cited by 70 publications

References 46 publications

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

The Chemistry of the 2‐Phosphaethynolate Anion

A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4−

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Formation of a Uranium-Bound η¹-Cyaphide (CP^–) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP^–)

A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO]⁴⁻