A 1D Coordination Polymer of UF<sub>5</sub> with HCN as a Ligand

Scheibe, Benjamin; Rudel, Stefan S.; Buchner, Magnus R.; Karttunen, Antti J.; Kraus, Florian

doi:10.1002/chem.201605293

Cited by 9 publications

(6 citation statements)

References 41 publications

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“…In general, protonation of metal‐bound cyano ligands (M−C≡N) at the terminal nitrogen atom leads to the corresponding metal complex with hydrogen isocyanide as a ligand (M−C≡N−H) + . In contrast, only a small number of metal complexes with hydrogen cyanide as a ligand are known (M−N≡C−H) . Although hydrogen isocyanide CNH is a good ligand for transition metals, it can be displaced by donor solvents (e.g.…”

Section: Methodsmentioning

confidence: 99%

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Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Sellin

Marvaud²,

Malischewski

2020

Angew Chem Int Ed

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Octacyanometalates K4[Mo(CN)8] and K4[W(CN)8] are completely protonated in superacidic mixtures of anhydrous hydrogen fluoride and antimony pentafluoride. The resulting hydrogen isocyanide complexes [Mo(CNH)8]4+ [SbF6]−4 and [W(CNH)8]4+ [SbF6]−4 are the first examples of eight‐coordinate homoleptic metal complexes containing hydrogen isocyanide (CNH) ligands. The complexes were crystallographically characterized, revealing hydrogen‐bonded networks with short N⋅⋅⋅H⋅⋅⋅F contacts. Low‐temperature NMR measurements in HF confirmed rapid proton exchange even at −40 °C. Upon protonation, ν(C≡N) increases of about 50 cm−1 which is in agreement with DFT calculations.

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Section: Methodsmentioning

confidence: 99%

“…[1,2] In contrast, only a small number of metal complexes with hydrogen cyanide as a ligand are known (MÀNCÀH). [3][4][5][6][7][8][9] Although hydrogen isocyanide CNH is a good ligand for transition metals, it can be displaced by donor solvents (e.g. water) or nucleophilic counteranions.…”

mentioning

confidence: 99%

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Sellin

Marvaud²,

Malischewski

2020

Angew Chem Int Ed

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“…Im Allgemeinen führt die Protonierung eines metallgebundenen Cyanids (M−C≡N) am terminalen Stickstoffatom zu dem entsprechenden Metall‐Isoblausäure‐Komplex (M−C≡N−H) + . Im Gegensatz dazu sind nur wenige Komplexe mit Blausäure‐Liganden (M−N≡C−H) + bekannt . Auch wenn Isoblausäure ein guter Ligand für Übergangsmetalle ist, so kann er trotzdem von donierenden Lösungsmitteln (z.…”

Section: Methodsunclassified

“…[1,2] Im Gegensatz dazu sind nur wenige Komplexe mit Blausäure-Liganden (M À N C À H) + bekannt. [3][4][5][6][7][8][9] Auch wenn Isoblausäure ein guter Ligand für Übergangsmetalle ist, so kann er trotzdem von donierenden Lçsungsmitteln (z. B. Wasser) oder von nukleophilen Gegenionen ersetzt werden.…”

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Isolierung und strukturelle Charakterisierung der achtfach protonierten Octacyanometallate [M(CNH)₈]⁴⁺ (M=Mo^IV,W^IV) aus Supersäuren

Sellin

Marvaud²,

Malischewski

2020

Angewandte Chemie

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Die Octacyanometallate K4[Mo(CN)8] und K4[W(CN)8] werden in der supersauren Mischung von wasserfreiem Fluorwasserstoff und Antimonpentafluorid vollständig protoniert. Die dabei entstandenen Komplexe [Mo(CNH)8]4+[SbF6]−4 und [W(CNH)8]4+[SbF6]−4 sind die ersten Beispiele für achtfach koordinierte homoleptische Komplexe mit Isoblausäure‐Liganden (CNH). Diese Verbindungen wurden kristallographisch untersucht und zeigen Netzwerke aus Wasserstoffbrückenbindungen mit kurzen N⋅⋅⋅H⋅⋅⋅F‐Kontakten. Tieftemperatur‐NMR‐Messungen in HF bestätigen einen schnellen Protonenaustausch sogar bei −40 °C. Durch die Protonierung steigt die Wellenzahl der ν(C≡N)‐Schwingung um etwa 50 cm−1, was im Einklang mit DFT‐Rechnungen steht.

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“…[28,29] Uranium pentafluoride,h owever, forms am onocapped-trigonal-prismatic adduct with 2,2'bipy; [30] UF 5 ·2 HCN insteadm anifests as ao ne-dimensional coordination polymer with trigonal-dodecahedral U V centres. [31] [WF 5 (NC 5 H 5 ) n ] + + (n = 2, 3)…”

Section: Molecular Structuresmentioning

confidence: 99%

Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂

Turnbull

Hazendonk

Wetmore

et al. 2020

Chemistry A European J

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The enhanced reactivity of [WF 5 ] + over WF 6 has been exploited to access an eutrald erivative of elusive WF 5 . The reactiono fW F 6 (NC 5 H 5 ) 2 with [(CH 3 ) 3 Si(NC 5 H 5 )][O 3 SCF 3 ]i n CH 2 Cl 2 results in quantitative formation of trigonal-dodecahedral [WF 5 (NC 5 H 5 ) 3 ] + ,w hich has been characterised as its [O 3 SCF 3 ] À salt by Ramans pectroscopy in the solid state and variable-temperature NMR spectroscopy in solution.T he salt is susceptible to slow decomposition in solution at ambient temperature via dissociation of ap yridyl ligand, and the resultant [WF 5 (NC 5 H 5 ) 2 ] + is reduced to WF 5 (NC 5 H 5 ) 2 in the presence of excess C 5 H 5 N, as determined by 19 FNMR spectrosco-py.P entagonal-bipyramidal WF 5 (NC 5 H 5 ) 2 was isolateda nd characterised by X-ray crystallography and Raman spectroscopy in the solid state, representing the first unambiguously characterised WF 5 adduct, as well as the first heptacoordinate adduct of at ransition-metal pentafluoride. DFT-B3LYP methodsh ave been used to investigatet he reduction of [WF 5 (NC 5 H 5 ) 2 ] + to WF 5 (NC 5 H 5 ) 2 ,s upporting at wo-electron reductiono fW VI to W IV by nucleophilic attack and diprotonation of ap yridyl ligand in the presence of free C 5 H 5 N, followed by comproportionation to W V .

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A 1D Coordination Polymer of UF₅ with HCN as a Ligand

Cited by 9 publications

References 41 publications

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Isolierung und strukturelle Charakterisierung der achtfach protonierten Octacyanometallate [M(CNH)₈]⁴⁺ (M=Mo^IV,W^IV) aus Supersäuren

Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂

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A 1D Coordination Polymer of UF5 with HCN as a Ligand

Cited by 9 publications

References 41 publications

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from Superacids

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from Superacids

Isolierung und strukturelle Charakterisierung der achtfach protonierten Octacyanometallate [M(CNH)8]4+ (M=MoIV,WIV) aus Supersäuren

Stabilisation of [WF5]+ and WF5 by Pyridine: Facile Access to [WF5(NC5H5)3]+ and WF5(NC5H5)2

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A 1D Coordination Polymer of UF₅ with HCN as a Ligand

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)₈]⁴⁺ (M=Mo^IV, W^IV) from Superacids

Isolierung und strukturelle Charakterisierung der achtfach protonierten Octacyanometallate [M(CNH)₈]⁴⁺ (M=Mo^IV,W^IV) aus Supersäuren

Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂