CC Bond Formation through Reductive Coupling of CS₂ to Yield Uranium Tetrathiooxalate and Ethylenetetrathiolate Complexes

Abstract

A novel twist: The UIII complex [((AdArO)3N)U] reacts with CS2 by reductive coupling to form the tetrathiooxalate complex [{((AdArO)3N)U}2(μ‐κ2:κ2‐C2S4)] with a newly formed CC bond (see scheme). The UIV/UIV tetrathiooxalate complex features a nonplanar C2S42− unit in an unprecedented μ‐κ2:κ2 binding mode. Further reduction gives the ethylenetetrathiolate complex [Na(dme)3]2[{((AdArO)3N)U}2(μ‐C2S4)]. DME=1,2‐dimethoxyethane.

Insight into the Reaction Mechanisms of (MeC5H4)3U with Isoelectronic Heteroallenes CS2, COS, PhN3, and PhNCO by DFT Studies: A Unique Pathway that Involves Bimetallic Complexes

“…The geometry of complex 8 was interesting because the two former CS 2 moieties were orthogonal to each other, which was very similar to the structure that was recently reported by Lam et al. for the reaction of [(( Ad ArO) 3 N)U] with CS 2 4c. However, in compound 8 , one CS 2 moiety was not stabilized by any interactions with the metal center, thus suggesting that its formation might be reversible.…”

Terminal Uranium(V/VI) Nitride Activation of Carbon Dioxide and Carbon Disulfide: Factors Governing Diverse and Well‐Defined Cleavage and Redox Reactions

“…[1] The former is an abundant, low-cost, and renewable C 1 source for fine chemicals and fuels production, [2] and the latter is av ersatile building block in organic synthesist hat is often used to model CO 2 reactivity. [3] In recent years f-elements, [4] and especially uranium, [5,6] have emerged as effective, appealing candidates for the reductive activation of CE 2 , [7] but studies of such activations remain in the shadow of those involving transition metals. [1][2][3]8] Metal nitride chemistry is now well-developed for transition metalsw ith aw ide range of reactivity types.…”

“…[10d] In contrast, [Nb{N(R)(Ar)} 3 (N)Na] 2 reacts with CO 2 to give [Nb{N(R)(Ar)} 3 (NCO 2 )][Na(THF) n ], but CÀOs plitting only occurs with addition of externale lectrophiles (such as Ac 2 O, O{C(O)CF 3 } 2 ,o rtBuCOCl);t his opens the door to eliminationo f the CO 2 -derived oxide as RCO 2 À and decarbonylation of the resulting niobium cyanate to niobium nitride to closeasynthetic cycle. [10b] Regarding uranium,apromisingc andidate in this arena given its redox chemistry, [5,6] it was not until recentlyt hat terminal uranium nitride complexes becamea vailable under ambient conditions, [11] and so their inherentr eactivity patterns are yet to be established. Indeed, there are no other classes of terminal f-blockn itrides available for reactivitys tudies, [12] and althoughanumber of bridgedd iuranium nitrides are emerging, [6a,b, 13] their reactivity is also almost unknown so determining and comparing the reactivity of terminal to bridgingu ranium nitrides would present opportunities to better understand their intrinsic reactivities.…”

Insights into the Mechanism of Reaction of [(C5Me5)2SmII(thf)2] with CO2 and COS by DFT Studies

“…[10][11] The reactivity of f-block-element complexes with COS and CS 2 has also been investigated experimentally. [8,[11][12][13][14][15] Several cases of the reactivity of a Sm II complex with CO 2 , CS 2 , or COS have been reported, for example, [(C 5 Me 5 ) 2 SmA C H T U N G T R E N N U N G (thf) 2 ] reductively coupled CO 2 in THF at room temperature to form the oxalate sandwich complex [{(C 5 Me 5 ) 2 Sm} 2 (m-h 2 :h 2 -O 2 CCO 2 )] in > 90 % yield. [8] Moreover, the same Sm II complex reacted with COS under identical conditions to generate the disproportionation product, [(C 5 Me 5 ) 2 Sm(m-h 2 :h 1 -S 2 CO)SmA C H T U N G T R E N N U N G (C 5 Me 5 ) 2 A C H T U N G T R E N N U N G (thf)].…”