Synthesis of the homoleptic rhodium(III) complex [Rh(C6Cl5)3]. Molecular structures of [Rh(C6Cl5)3] and [Rh(C6Cl4–C6Cl4)(C6Cl5)(SC4H8)2]

García, Manuel Sánchez; Jiménez, M. Victoria; Lahoz, Fernando J.; López, José A.; Oro, Luis A.

doi:10.1039/a806538a

Cited by 10 publications

(11 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Given this precedent, we rationalized that the [C 6 Cl 5 ] − ligand could also stabilize homoleptic U(IV) and Th(IV) complexes. Additional support for this hypothesis comes from the large number of homoleptic transition metal perhalophenyl complexes that have been reported over the past 25 years. − Despite these past synthetic achievements, however, no homoleptic perhalophenyl complexes are known for actinides. Additionally, the only heteroleptic perhalophenyl actinide complexes are the aforementioned uranyl(VI) species, making this a potentially fruitful avenue of investigation.…”

Section: Introductionmentioning

confidence: 99%

Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Ordoñez

Autschbach

et al. 2021

Inorg. Chem.

View full text Add to dashboard Cite

The reaction of AnCl 4 (DME) n (An = Th, n = 2; U, n = 0) with 5 equiv of LiC 6 Cl 5 in Et 2 O resulted in the formation of homoleptic actinide-arylSimilarly, the reaction of AnCl 4 (DME) n (An = Th, n = 2; U, n = 0) with 3 equiv of LiC 6 Cl 5 in Et 2 O resulted in the formation of heteroleptic actinide-aryl). Density functional calculations show that the An−C ipso σbonds are considerably more covalent for the uranium complexes vs the thorium analogues, in line with past results. Additionally, good agreement between experiment and calculations is obtained for the 13 C ipso NMR chemical shifts in [Li][1] and [Li][3]. The calculations demonstrate a deshielding by ca. 29 ppm from spin−orbit coupling effects originating at Th, which is a direct consequence of 5f orbital participation in the Th−C bonds.

show abstract

Section: Introductionmentioning

confidence: 99%

Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Ordoñez

Autschbach

et al. 2021

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…[23] Recognizing that reduction of the uraniumc enterw as a major impediment to previoussynthetic attempts, we attempted to ligate the percholorophenyl fragment, [C 6 Cl 5 ] À ,t ou ranyl, because it is am uch poorer reducing agent than most other alkylating agents, and thus should not as readily reduce the high-valent U 6 + centeri nu ranyl. [26] Homoleptic and heteroleptic perhalophenyl complexes are knownf or aw ide varietyo f transition metals, [26][27][28][29][30][31][32][33][34][35][36] [2]). A dditionally,w ea nalyze their electronic structures and 13 CNMR spectra by relativistic density functional theory (DFT) calculations, which enabled us to identify the degree of participation of the 5f subshell in the uranium-carbon bonds.…”

mentioning

confidence: 99%

“…[23] Recognizing that reduction of the uraniumc enterw as a major impediment to previoussynthetic attempts, we attempted to ligate the percholorophenyl fragment, [C 6 Cl 5 ] À ,t ou ranyl, because it is am uch poorer reducing agent than most other alkylating agents, and thus should not as readily reduce the high-valent U 6 + centeri nu ranyl. [26] Homoleptic and heteroleptic perhalophenyl complexes are knownf or aw ide varietyo f transition metals, [26][27][28][29][30][31][32][33][34][35][36] yet no reported perhalophenyl complexes are knownf or actinides, making this ap otentially fruitful avenue of investigation. Herein, we describe the synthesis and characterization of the first structurally characterized uranyl aryl complexes,[ Li(Et 2 O) 2 (THF)][UO 2 (C 6 Cl 5 ) 3 ]( [Li] [1]) and [Li(THF) 4 ][UO 2 (C 6 Cl 5 ) 3 (THF)] ([Li] [2]).…”

mentioning

confidence: 99%

Synthesis and Characterization of Two Uranyl‐Aryl “Ate” Complexes

Ordoñez

Autschbach

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

Reaction of [UO2Cl2(THF)3] with 3 equivalents of LiC6Cl5 in Et2O resulted in the formation of first uranyl aryl complex [Li(Et2O)2(THF)][UO2(C6Cl5)3] ([Li][1]) in good yields. Subsequent dissolution of [Li][1] in THF resulted in conversion into [Li(THF)4][UO2(C6Cl5)3(THF)] ([Li][2]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][1] and [Li][2] exhibit appreciable covalency. Additionally, the 13C NMR chemical shifts for their Cipso environments are strongly affected by spin‐orbit coupling—a consequence of 5f orbital participation in the U−C bonds.

show abstract

“…14). 48 Even the SPY -5 geometry found for the pentafluorophenyl derivative [Rh III (C 6 F 5 ) 5 ] 2− (Table 2; Fig. 8) 35 can be envisaged as deriving from the OC-6 structure with a vacant coordination site-as in the related d 3 species [Cr III (C 6 F 5 ) 5 ] 2− (see above).…”

Section: Stereochemistrymentioning

confidence: 95%

“…Thus, the geometries of the heavy-metal derivatives [Rh III (C 6 Cl 5 ) 4 ] − and [Pt IV (C 6 Cl 5 ) 4 ] are based upon an OC-6 arrangement (Table1; Fig.7) 43,47 and are similar to that of the isoleptic d 3 species [Cr III (C 6 Cl 5 ) 4 ] − commented above. In a similar way, the structure of the neutral compound [Rh III (C 6 Cl 5 ) 3 ] can be described as an OC-6 arrangement of the three chelating C 6 Cl 5 -jC,jCl 2 ligands in a facial mode (Table1; Fig.14) 48. Even the SPY -5 geometry found for the pentafluorophenyl derivative [Rh III (C 6 F 5 ) 5 ] 2− (Table2; Fig.8)35 can be envisaged as deriving from the OC-6 structure with a vacant…”

mentioning

confidence: 99%

New advances in homoleptic organotransition-metal compounds: The case of perhalophenyl ligands

et al. 2007

View full text Add to dashboard Cite

Homoleptic derivatives of formula [M(C(6)X(5))(n)](z-) (X = F, Cl) have been prepared and isolated for every first-row transition metal as well as for several of the heavier ones. The stoichiometry attained in each case (n ranging between 2 and 6) can be understood considering the tendency of a given metal ion to compensate its coordinative and electronic unsaturation, while not incurring severe interligand repulsive effects. The molecular structures associated with each stoichiometry seem, in turn, to be governed by electronic rather than steric factors. Most of these [M(C(6)X(5))(n)](z-) compounds are unsaturated, open-shell organometallic species, not fulfilling the 18-electron (or Effective Atomic Number) rule. This behaviour can be attributed to the absence of pi stabilising ligands (such as CO, phosphines, alkenes, alkynes, a variety of substituted aromatic rings, and so on) which are otherwise ubiquitous in organotransition-metal chemistry. The magnetic properties of the [M(C(6)X(5))(n)](z-) species have been determined by EPR spectroscopy and/or bulk magnetisation measurements. Excellent correlation between molecular geometry and magnetic properties (whether diamagnetic or paramagnetic) has been observed. Many of these compounds undergo chemically- or electrochemically-induced electron exchange processes. These redox reactions proceed without alteration in the stoichiometry of the [M(C(6)X(5))(n)](z-) compound, but usually involve a sharp change in the molecular geometry according to the different electron configuration of the interrelated species.

show abstract

Synthesis of the homoleptic rhodium(III) complex [Rh(C6Cl5)3]. Molecular structures of [Rh(C6Cl5)3] and [Rh(C6Cl4–C6Cl4)(C6Cl5)(SC4H8)2]

Cited by 10 publications

References 20 publications

Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Synthesis and Characterization of Two Uranyl‐Aryl “Ate” Complexes

New advances in homoleptic organotransition-metal compounds: The case of perhalophenyl ligands

Contact Info

Product

Resources

About