“…The latter complexes were prepared by the reaction of Cp*ReCl 4 with polychalcogenide ligands Na 2 S 4 and (NEt 4 ) 2 Se 6 , respectively. Other related Cp or Cp*Re complexes with sulfide or polysulfide ligands have also been characterized. − 1 Perspective drawing and numbering scheme for Cp‘Re(η 2 -S 3 )Cl 2 , 2 . Thermal ellipsoids are shown at the 50% probability level.…”
The reaction of Cp′ReCl 4 (Cp′ ) EtMe 4 C 5 ) with 2-3 equiv of bis(trimethylsilyl)sulfide in chloroform in the presence of an oxidant results in the formation of Cp′Re(η 2 -S 3 )Cl 2 , 2. Complex 2 has been characterized by spectroscopic methods, and its structure has been confirmed by an X-ray diffraction study. Complex 2 reacts with hydrogen under mild conditions to form H 2 S, HCl, and a rhenium product tentatively identified as (Cp′Re) 2 S 4 , 3. Complex 3 reacted with benzyl bromide to form [(Cp′Re) 2 (µ-S 2 )(µ-SCH 2 Ph) 2 ]Br 2 , 4, which has been completely characterized by spectroscopic studies and an X-ray crystal structure. The structures and reactions of the Cp′Re derivatives with sulfur ligands are compared to those of the related tetrasulfur-bridged CpMo derivatives.Supporting Information Available: Tables giving crystal data, positional and thermal parameters, bond distances, and bond angles for 2 and 4. This material is available free of charge via the Internet at http://pubs.acs.org. OM000962E
“…The latter complexes were prepared by the reaction of Cp*ReCl 4 with polychalcogenide ligands Na 2 S 4 and (NEt 4 ) 2 Se 6 , respectively. Other related Cp or Cp*Re complexes with sulfide or polysulfide ligands have also been characterized. − 1 Perspective drawing and numbering scheme for Cp‘Re(η 2 -S 3 )Cl 2 , 2 . Thermal ellipsoids are shown at the 50% probability level.…”
The reaction of Cp′ReCl 4 (Cp′ ) EtMe 4 C 5 ) with 2-3 equiv of bis(trimethylsilyl)sulfide in chloroform in the presence of an oxidant results in the formation of Cp′Re(η 2 -S 3 )Cl 2 , 2. Complex 2 has been characterized by spectroscopic methods, and its structure has been confirmed by an X-ray diffraction study. Complex 2 reacts with hydrogen under mild conditions to form H 2 S, HCl, and a rhenium product tentatively identified as (Cp′Re) 2 S 4 , 3. Complex 3 reacted with benzyl bromide to form [(Cp′Re) 2 (µ-S 2 )(µ-SCH 2 Ph) 2 ]Br 2 , 4, which has been completely characterized by spectroscopic studies and an X-ray crystal structure. The structures and reactions of the Cp′Re derivatives with sulfur ligands are compared to those of the related tetrasulfur-bridged CpMo derivatives.Supporting Information Available: Tables giving crystal data, positional and thermal parameters, bond distances, and bond angles for 2 and 4. This material is available free of charge via the Internet at http://pubs.acs.org. OM000962E
“…A large number of transition metal‐polysulfido compounds have been reported and a detailed discussion on the synthesis, structural diversity and reactivity of such compounds may be found elsewhere [19f,20] . Many of these reported compounds are, however, organometallic compounds [20a,c,d,f,n,p,r–t] …”
A new mononuclear cobalt(III)‐pentasulfido compound, [(L)Co(S5)] (3) has been synthesized by using a convergent redox reaction between elemental sulfur and two new cobalt(II)‐thiolato compounds, [(L)Co(SR)] (R=Ph, 2 a; 2,6‐Me2‐C6H4, 2 b), which in turn were synthesized from a dimeric cobalt(II) complex, [(L)2Co2]2+ (1). Compound 3 features a low‐spin, diamagnetic, Co(III) center with a coordinated pentasulfido (S52−) chain and has no precedence in the literature. Compound 3 is highly stable towards reduction with a potential of −1.36 V (vs. Cp2Fe+/Cp2Fe) and gives back 1 upon chemical/electrochemical reduction. Reaction of 3 with phosphines yields back 1 and phosphine sulfides, while protonation of the coordinated S52− chain in 3 leads to the formation of 1, elemental sulfur and H2S. Finally, transfer of the coordinated S52− chain in 3 to selected organic compounds, such as MeI, PhCH2Br and PhCOCl, for the generation of organopolysulfido compounds has been demonstrated.
“…Although MS 5 complexes are known for both rare‐earth and actinide metals, complexes 8 a and 8 b are apparently the only examples of such a simple MS 4 unit involving an f block element. Although the mixed polysulfide nature of 8 is unusual, “M(S x )(S y )” complexes have been reported elsewhere as exemplified by Cp*Re(S 3 )(S 4 ) [64] and [PPh 4 ][In(S 4 )(S 6 )Cl] [65]…”
Exploration of the reduction chemistry of the 2,2’‐bipyridine (bipy) lanthanide metallocene complexes Cp*2LnCl(bipy) and Cp*2Ln(bipy) (Cp* = C5Me5) resulted in the isolation of a series of complexes with unusual composition and structure including complexes with a single Cp* ligand, multiple azide ligands, and bipy ligands with close parallel orientations. These results not only reveal new structural types, but they also show the diverse chemistry displayed by this redox‐active platform. Treatment of Cp*2NdCl(bipy) with excess KC8 resulted in the formation of the mono‐Cp* Nd(III) complex, [K(crypt)]2[Cp*Nd(bipy)2], 1, as well as [K(crypt)][Cp*2NdCl2], 2, and the previously reported [K(crypt)][Cp*2Nd(bipy)]. A mono‐Cp* Lu(III) complex, Cp*Lu(bipy)2, 3, was also found in an attempt to make Cp*2Lu(bipy) from LuCl3, 2 equiv. of KCp*, bipy, and K/KI. Surprisingly, the (bipy)1− ligands in neighboring molecules in the structure of 3 are oriented in a parallel fashion with intermolecular C⋅⋅⋅C distances of 3.289(4) Å, which are shorter than the sum of van der Waals radii of two carbon atoms, 3.4 Å. Another product with one Cp* ligand per lanthanide was isolated from the reaction of [K(crypt)][Cp*2Eu(bipy)] with azobenzene, which afforded the dimeric Eu(II) complex, [K(crypt)]2[Cp*Eu(THF)(PhNNPh)]2, 4. Attempts to make 4 from the reaction between Cp*2Eu(THF)2 and a reduced azobenzene anion generated instead the mixed‐valent Eu(III)/Eu(II) complex, [K(crypt)][Cp*Eu(THF)(PhNNPh)]2, 5, which allows direct comparison with the bimetallic Eu(II) complex 4. Mono‐Cp* complexes of Yb(III) are obtained from reactions of the Yb(II) complex, [K(crypt)][Cp*2Yb(bipy)], with trimethylsilylazide, which afforded the tetra‐azido [K(crypt)]2[Cp*Yb(N3)4], 6, or the di‐azido complex [K(crypt)]2[Cp*Yb(N3)2(bipy)], 7 a, depending on the reaction stoichiometry. A mono‐Cp* Yb(III) complex is also isolated from reaction of [K(crypt)][Cp*2Yb(bipy)] with elemental sulfur which forms the mixed polysulfido Yb(III) complex [K(crypt)]2[Cp*Yb(S4)(S5)], 8 a. In contrast to these reactions that form mono‐Cp* products, reduction of Cp*2Yb(bipy) with 1 equiv. of KC8 in the presence of 18‐crown‐6 resulted in the complete loss of Cp* ligands and the formation of [K(18‐c‐6)(THF)][Yb(bipy)4], 9. The (bipy)1− ligands of 9 are arranged in a parallel orientation, as observed in the structure of 3, except in this case this interaction is intramolecular and involves pairs of ligands bound to the same Yb atom. Attempts to reduce further the Sm(II) (bipy)1− complex, Cp*2Sm(bipy) with 2 equiv. of KC8 in the presence of excess 18‐crown‐6 led to the isolation of a Sm(III) salt of (bipy)2− with an inverse sandwich Cp* counter‐cation and a co‐crystallized K(18‐c‐6)Cp* unit, [K2(18‐c‐6)2Cp*]2[Cp*2Sm(bipy)]2 ⋅ [K(18‐c‐6)Cp*], 10.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
