[{Rh2Cp(μ‐CH2)2}2(μ‐S4)]2+: A Novel Tetranuclear Cationic Complex with a Rectangular S4 Unit

Isobe, Kiyoshi; Ozawa, Yoshiki; Miguel, Amelio Vázquez de; Zhu, Tao; Zhao, Kui‐Ming; Nishioka, Takanori; Ogura, Takashi; Kitagawa, Teizo

doi:10.1002/anie.199418821

Cited by 40 publications

(20 citation statements)

References 15 publications

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“…Complex 1 , [Rh 2 Cp* 2 (μ 2 -CH 2 ) 2 (μ 2 -SH)](BPh 4 ), has three characteristic functionalities of the Rh(μ-SH)Rh group: the Rh−Rh single bond and two μ 2 -CH 2 groups. By primarily using the Rh(μ-SH)Rh functionality, we have discovered its unique reactivities toward electrophiles such as O 2 , Ag + , and unsaturated hydrocarbons . We now use all three functionalities of 1 to synthesize complex 3 .…”

mentioning

confidence: 99%

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Nishioka¹,

Isobe²,

Einoshita³

et al. 1998

Organometallics

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Deprotonation of the double-bridging μ2-CH2 complex [Rh2Cp*2(μ2-CH2)2(μ2-SH)](BPh4) (Cp* = η5-C5Me5) with [Rh2Cp*2(μ2-OH)3](BPh4) led to the isolation of the trirhodium μ3-S complex [Rh3Cp*3(μ3-η2-||-C2H2)(μ3-S)](BPh4)2, including an acetylene ligand generated by a unique C−C bond coupling and deprotonation of two μ2-CH2 groups. The dynamic property of the acetylene complex in both solution and the solid state was studied by variable-temperature 1H, 13C, and CP/MAS 13C NMR spectroscopy.

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confidence: 99%

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Nishioka¹,

Isobe²,

Einoshita³

et al. 1998

Organometallics

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“…Sulfur is known to form catenanes, including the S 4 2anion, in a large number of compounds. [27][28][29][30][31][32] Thus far, no η 5 -Cp iron-sulfur clusters with S x groups, x > 2, have been reported.…”

Section: Resultsmentioning

confidence: 99%

Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)

et al. 1997

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The synthesis and characterization of iron-sulfur clusters stabilized by dimethylsilyl-bridged cyclopentadienyl groups are reported. The thermal reaction of Me(2)Si(eta(5)-C(5)H(4))(2)Fe(2)(CO)(4) (1) with S(8) yields the tetranuclear cubane-type cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6) (4) and the pentanuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(5)S(12) (3) in high yields. The photochemical reaction of 1 with S(8) yields the tetranuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6)(CO) (5), which contains one residual terminal carbonyl. The crystal structures of 3 and 4 have been determined. Crystal data: 3.CH(2)Cl(2), monoclinic, C2/c, a = 23.480(13) Å, b = 11.192 (4) Å, c = 17.84 (3) Å, beta = 118.58(9) degrees, V = 4118(7) Å(3), Z = 4, R = 0.078; 4, triclinic, P&onemacr;, a = 8.4787(7) Å, b = 12.9648(9) Å, c = 13.4990(9) Å, alpha = 79.857(8) degrees, beta = 75.293(8) degrees, gamma = 74.041(11) degrees, V = 1370.9(2) Å(3), Z = 2, R = 0.0447. The Fe(5)S(12) core of 3 has a bowtie structure in which a central iron atom is octahedrally coordinated by six sulfur atoms from one tetrasulfido and four disulfido groups. The structure of 4 resembles the structure of the known iron-sulfur cluster Cp(4)Fe(4)S(6). However, 4 shows a markedly enhanced thermal stability compared to Cp(4)Fe(4)S(6). In their cyclic voltammograms, 4 and 5 exhibit electrochemical behavior typical of cubane-type Cp-iron-sulfur clusters, whereas the cyclic voltammogram of 3 is quite different. The nu(CO) mode of 5 has been measured for four different oxidation states of the cluster by means of IR spectroelectrochemical methods. The Mössbauer spectra of 3 and 3(+) are in accordance with their pentanuclear structure.

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“…5 In 1994 and 2004, we had chances to find two kinds of rectangular S 4 shapes in metal complexes of [{Cp*M(®-CH 2 )} 2 (®-S 4 )]X 2 (Cp*: © 5 -C 5 Me 5 , M = Rh and Ir, X = halides and other counter anions) which were characterized by X-ray analysis. 6,7 Stimulated by our findings the Mealli and Hoffmann group has done theoretical studies of the two complexes and clarified that both S 4 units are stable forms and two disulfide units form an unusual S 4 2¹ rectangle through a two-electron oxidation of two disulfide S 2 2¹ . 8,9 Oxidation of elemental sulfur by certain powerful oxidants in solvents of low basicity produces the square-planar colorless cation S 4 2+ which is isolated in crystalline salts with various anions and characterized, inter alia, by X-ray crystallography and theoretical calculation.…”

Section: ç Introductionmentioning

confidence: 82%

“…6 The X-ray analysis revealed the structure of 1, which is shown without the counter anions in Figure 5a. The rectangular planar S 4 unit bridges two Rh 2 (®-CH 2 ) 2 groups to form a Rh 4 S 4 eight-membered ring with a centrosymmetric chair-like core.…”

Section: ç Rectangular S 4 Species In Metal Complexesmentioning

confidence: 99%

Chemistry of Tetrasulfur Including Mysterious Rectangular S4 Metal Complexes

Isobe¹

2011

Chemistry Letters

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Of eleven possible isomers for neutral S 4 , rectangular S 4 has been proposed theoretically as one of the most stable forms. There has, however, been no consensus as to the S 4 ground-state geometric structure despite much effort over recent years, because of the lack of direct structural information from experimental work due to lack of preparation in a pure state. The principal question is whether the ground-state geometry is rectangular D 2h or open planar C 2v . Our group found first rectangular S 4 in coordination compounds of Rh and Ir tetranuclear complexes as a ligand and disclosed mysterious rectangular S 4 by X-ray analysis and theoretical studies. Here, the newly developed chemistry of rectangular S 4 complexes together with the related tetrasulfur species is introduced both from experimental and theoretical view points. In addition, more accurate argument of the principal question mentioned above is also described using results obtained from recent high-level theoretical calculations.

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[{Rh₂Cp(μ‐CH₂)₂}₂(μ‐S₄)]²⁺: A Novel Tetranuclear Cationic Complex with a Rectangular S₄ Unit

Cited by 40 publications

References 15 publications

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)

Chemistry of Tetrasulfur Including Mysterious Rectangular S4 Metal Complexes

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[{Rh2Cp(μ‐CH2)2}2(μ‐S4)]2+: A Novel Tetranuclear Cationic Complex with a Rectangular S4 Unit

Cited by 40 publications

References 15 publications

Formation and Dynamic Properties of the Triangular Rhodium μ3-Sulfido Complex [Rh3Cp*3(μ3-η2-||-C2H2)(μ3-S)]2+ (Cp* = η5-C5Me5), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Formation and Dynamic Properties of the Triangular Rhodium μ3-Sulfido Complex [Rh3Cp*3(μ3-η2-||-C2H2)(μ3-S)]2+ (Cp* = η5-C5Me5), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Iron−Sulfur Clusters with SiMe2-Bridged Cyclopentadienyl Ligands: [Me2Si(η5-C5H4)2]2Fe5S12, [Me2Si(η5-C5H4)2]2Fe4S6, and [Me2Si(η5-C5H4)2]2Fe4S6(CO)

Chemistry of Tetrasulfur Including Mysterious Rectangular S4 Metal Complexes

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[{Rh₂Cp(μ‐CH₂)₂}₂(μ‐S₄)]²⁺: A Novel Tetranuclear Cationic Complex with a Rectangular S₄ Unit

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Formation and Dynamic Properties of the Triangular Rhodium μ₃-Sulfido Complex [Rh₃Cp₃(μ₃-η²-||-C₂H₂)(μ₃-S)]²⁺ (Cp = η⁵-C₅Me₅), Including an Acetylene Ligand Generated by the Coupling and Deprotonation of Two Bridging Methylene Units in a Dirhodium Complex

Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)