Facile N-functionalization and strong magnetic communication in a diuranium(<scp>v</scp>) bis-nitride complex

Barluzzi, Luciano; Chatelain, Lucile; Fadaei‐Tirani, Farzaneh; Živković, Ivica; Mazzanti, Marinella

doi:10.1039/c8sc05721d

Cited by 39 publications

(48 citation statements)

References 128 publications

(50 reference statements)

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“…Only the use of the N2O adduct of the N-heterocyclic carbene 1,3-dimesitylimidazol-2ylidene (IMes) IMesN2O 52 in THF at -80°C (Scheme 13) allowed the synthesis of the oxo-bridged diuranium(IV) complex [{U(OSi(O t Bu)3)3}2(μ-O)], 21, in 79% yield. 53 The ability of the IMesN2O to selectively produce the oxodiuranium(IV) complex could be due to the higher reaction rates of this reagent 54 compared to the other used oxygen transfer agents.…”

Section: Reaction With Chalcogen Transfer Reagents; Synthesis Of Chalmentioning

confidence: 99%

“…The diuranium(V) bis(nitride) 28 demonstrated high nucleophilic reactivity towards diverse small molecules which is summarized in Scheme 19. 53 The reactivity of a toluene solution of 28 with one equiv of CS2 led to CS2 cleavage affording the sulfide-thiocyanate complex [K2{[U(OSi(O t Bu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 35. Cleavage of CS2 and concomitant formation of NCSwas also observed for the U(IV) bridging nitride 29 (see next section) and for U(V) and U(VI) terminal nitrides.…”

Section: Reactivity Of Uranium(v) Nitride Bridged Complexesmentioning

confidence: 99%

“…Thus, both ligand-based and metalbased reactivity are observed. The formation of thiocyanate, cyanate, and cyanide was confirmed by structural studies and 13 C NMR analysis of the products after reaction with 13 CS2, 13 CO2 and 13 CO. 53 The complete cleavage of the CO triple bond (one of the strongest bonds in nature) in ambient conditions is particularly remarkable and is probably the result of the cooperative binding of CO by the two metal centres. Notably, CO cleavage is not observed in the reaction of terminal nitrides with CO which leads to reductive carbonylation.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

“…75 The reactivity of complex 28 with 1 atm of H2 in ambient conditions is remarkable in that the bis-nitride effects the oxidative cleavage of H2 in mild conditions to yield the bis-imido complex [KU(µ-NH)(OSi(O t Bu)3)]2, 38. 53 Notably, cleavage of H2 by metal-nitride is a rarely observed event. The reaction pathway probably does not involve H2 coordination to the metal centre but direct attack of H2 to the two nucleophilic nitrides as previously reported for a terminal iridium complex.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

2019

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Section: Reaction With Chalcogen Transfer Reagents; Synthesis Of Chalmentioning

confidence: 99%

Section: Reactivity Of Uranium(v) Nitride Bridged Complexesmentioning

confidence: 99%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

2019

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“…The only site of significant change is in the Cr-N pz bonds, due in partt ot heir interaction with K + in [K 2 (THF) 4 Cr 2 L 2 (BCC)],asw ellast he change from Cr III to Cr II . 17; Cr1ÀN3: 2.0509 17;Cr1ÀN5:2 .0693 16; Cr1ÀN11: 2.0556 16; Cr2ÀN4:2 .4461 16; Cr2ÀN6:2 .0845(16);C r2ÀN8:2.0497 (16);Cr2ÀN10:2 .0722 (16);Cr2ÀN12: 2.0634 (16);N 3-Cr1-N11: 160.03(7); N8-Cr2-N12:155.75 (6)…”

Section: [K 2 (Thf) 4 Cr 2 L 2 (Bcc)]mentioning

confidence: 99%

A Dimeric Chromium(II) Pincer as an Electron Shuttle for N=N Bond Scission

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Caulton

2020

Chemistry A European J

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Reduction of the bis-pyrazolyl pyridine complex [CrL] 2 with 4KC 8 ,f ollowed by addition of one azobenzene (overall mole ratio 1:4:1), PhNNPh, transfers reducing equivalents to three azobenzenes, to form [K 3 Cr(PhNNPh) 3 ]. This has three k 2 PhNNPh 2À ligands and K + bound to nitrogen atoms of azobenzene. When the stoichiometry is modified to 1:4:3, the product is changed to [K 2 CrL(PhNNPh) 2 ], which has C 2 symmetry except for the intimate ion pairingo ft wo K + ions to reduceda zobenzene nitrogen atoms, andt op yrazolate and phenylr ings. The origin of the observed delivery of reducinge quivalents to several, not to as ingle N=N bond, is traced to the resistance of the one-electron-reduced substrate to receiving as econd electron, and is thus ag eneral phenomenon. [CrL] 2 alone is shown to be atwo-electron reductant towards benzo[c]cinnoline (BCC) resulting in a product of formula [Cr 2 L 2 (BCC)],i nw hich the reducing equivalents originate purely from Cr II .A na nalogous study of the reaction of [CrL] 2 with azobenzene yields [Cr 2 L 2 (PhNNPh)(THF)],a na dduct in whicho ne THF has displaced one of four hydrazide nitrogen/Cr bonds.T ogether these illustrate different modes for the Cr 2 L 2 unit to bind and reduce the N=Nb ond. Collectively,t heser esultss how that two divalentC r, without added K 0 ,h avet he ability to reduce the N=Nb ond. Further KC 8 reduction of preformed Cr 2 L 2 (RNNR) inevitably gives products in which K + stabilizes the charge in the increasingly electron-rich nitrogena toms, in ap henomenonw hich mimics proton coupled electron transfer:K + performs the role of H + .Aleast-squares fit of the two singlyr educed DFT structures shows that the only major change is ar e-orientationo fo ne of the two phenyl rings in ordert oa void repulsion with potassium but to still allow interaction of that phenyl p system with K + .T his shows both the impact of K + ,b eing modestt on itrogen/ chromium interactions, but nevertheless accommodating some p donation of phenyl to potassium. Finally,d elivering increasing equivalents of KC 8 leads to complete cleavage of the N=Nb ond, and both Nb ind to three Cr II .T he varied impacts of the K + electrophile on NN multiple bond reduction is discussed.

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Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

et al. 2023

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Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

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Facile N-functionalization and strong magnetic communication in a diuranium(v) bis-nitride complex

Cited by 39 publications

References 128 publications

Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

A Dimeric Chromium(II) Pincer as an Electron Shuttle for N=N Bond Scission

Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

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