Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM′Re<sub>2</sub>S<sub>4</sub> Cubanes (M = Ir, Rh, Ru; M′ = Pt, Pd)

Shibata, Rie; Seino, Hidetake; Fujii, Shunpei; Mizobe, Yasushi

doi:10.1021/ic100339f

Cited by 4 publications

(1 citation statement)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The M 4 E 4 cubane framework is a recurring structural motif that has incorporated metals from every part of the periodic chart, linked by an equally diverse range of anions. Given their abundance, it is not surprising to find that cubanes have been involved in a wide range of important processes, from the active site of photosynthesis and as catalysts in water splitting, to low-temperature CVD synthesis of novel solid-state phases .…”

Section: Introductionmentioning

confidence: 99%

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

et al. 2017

View full text Add to dashboard Cite

Tetrametallic thorium compounds with a ThE core (E = S, Se) having a distorted cubane structure can be prepared by ligand-based reductions of elemental E with thorium chalcogenolates, prepared by in situ oxidation of Th metal with a 3:1 mixture of PhEEPh and FCEECF. Four compounds, (py)ThS(μ-SPh)(SCF), (py)ThS(μ-SPh)(SeCF), (py)ThSe(μ-SePh)(SeCF), and (py)ThSe(μ-SePh)(SCF), were isolated and characterized by NMR spectroscopy and X-ray diffraction. These compounds clearly demonstrate the chemical impact of ring fluorination, with the less-nucleophilic ECF ligands occupying the terminal binding sites and the EPh ligands bridging two metal centers. For this series of compounds, crystal packing and intermolecular π···π and H-bonding interactions result in a consistent motif and crystallization in a body-centered tetragonal unit cell. Solution-state Se NMR spectroscopy reveals that the solid-state structures are maintained in pyridine.

show abstract

Section: Introductionmentioning

confidence: 99%

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

et al. 2017

View full text Add to dashboard Cite

show abstract

An Iodido‐Bridged Dimer of Cubane‐Type RuIr₃S₄ Cluster: Structural Rearrangement to New Octanuclear Core and Catalytic Reduction of Hydrazine

et al. 2019

View full text Add to dashboard Cite

Nitrogen‐fixing enzymes contain octanuclear metal–sulfur clusters at the active site, which are constructed on the basis of combined two cubic M4S3C skeletons. In this study, the dimer of cubane‐type RuIr3S4 cluster [{(Cp*Ir)3(µ3‐S)4Ru}2(µ2‐I)3]I (2: Cp* = η5‐C5Me5) was synthesized via oxidation of [(Cp*Ir)3(µ3‐S)4(CymRu)] (Cym = η6‐p‐iPrC6H4Me) with I2 followed by ligand exchange. Two cubane cores are bridged by three iodido ligands in 2, while these cubes are fused into a unique Ru2Ir6S8 framework by 2e‐reductuion to give [(Cp*Ir)6Ru2(µ3‐S)8][I]2. Addition of excess PhNHNH2 to 2 cleaved the dimer structure to form the hydrazine adduct of single cubane [(Cp*Ir)3(µ3‐S)4{RuI(NH2NHPh)2}]I. Reduction of N2H4 with Cp2Co and [HNEt3][BF4] was catalyzed by 2 in much higher rate than disproportionation of N2H4. The molecular structures of all new cluster compounds were characterized by X‐ray diffraction studies.

show abstract

Organo-transition metal cluster complexes

Humphrey¹,

Cifuentes²

2012

Organometallic Chemistry

View full text Add to dashboard Cite

The number of c.v.e. donated by m 3 -alkenyl and m 4 -alkyne ligands has been examined using fragment molecular orbital (FMO) calculations on two representative clusters, Ru 3 (m 3 -H 2 NNH)(m 3 -CHCH 2 )(m-CO)(CO) 7 and Ru 4 (m 4 -HC 2 H)(CO) 12 . Results suggest donation of three and four electrons, respectively, the observed stability of these unsaturated clusters attributed to the large HOMO-LUMO gaps. 8 DFT calculations on the series of triosmium-fullerene complexes Os 3 (m 3 -Z 2 :Z 2 :Z 2 -C 60 )(CO) 8 L (L = CO, PMe 3 ) and their anions (À1 to À4) show that all three metal atoms are p-coordinated to the C 6 unit of the fullerene in the neutral, mono-and dianionic complexes, but consist of mixed s-p-coordination in the tri-and tetraanionic cases, affording [Os 3 (m 3 -Z 2 :Z 2 :Z 1 -C 60 )(CO) 8 L] 3À and [Os 3 (m 3 -Z 2 :Z 1 :Z 1 -C 60 )-(CO) 8 L] 4À . 9 Interstitial nickel and palladium atoms in icosahedral and pentagonal antiprismatic clusters with five-fold symmetry have been shown to be analogous to endohedral noble gas atoms in fullerenes. 10 The electronic structure and bonding of the omnicapped truncated tetrahedral Au 20 cluster has been examined, its large band gap (1.77 eV) rationalized, and its structure related to those of other M 20 complexes. 11 4 Structural studies A single-crystal neutron diffraction study of Co 4 (m 3 -H) 4 (Z 5 -C 5 Me 4 Et) 4 has revealed the presence of four face-capping hydride ligands. 12 5 High-nuclearity clusters 5.1 Homonuclear high-nuclearity clusters The dinitrido cluster tetraanion [Co 10 (m 6 -N) 2 (CO) 19 ] 4À can be chemically or electrochemically oxidized to give [Co 11 (m 6 -N) 2 (CO) 21 ] 3À (2) via three spectroscopicallyidentified intermediates. The 154 c.v.e. cluster contains a bent bioctahedral metal cage with 10 of the carbonyl ligands bridging Co-Co bonds and has four excess electrons; cyclic voltammetry indicates reversible loss of two electrons. 13 Reaction of Pd 10 (CO) 12 (PEt 3 ) 6 with Pd 2 (dba) 3 (dba = dibenzylideneacetone) or [Pd(NCMe) 4 ] 2+ affords Pd 52 (CO) 36 (PEt 3 ) 14 (ca. 5%) or Pd 66 (CO) 45 (PEt 3 ) 16 (13%), respectively. The clusters can be considered to be derived from a common Pd 38 core via condensation of Pd 7 caps and form mixed ccp/hcp layered structures. 14 [Pt 38 (CO) 44 ] 2À has been prepared in high yield by carbonylation (800 mmHg) of [PtCl 6 ] 2À salts in water; a similar carbonylation at 900 mmHg affords quantitative yields of [Pt 3n (CO) 6n ] 2À (n 4 6). 15 The double salt Ag 12 (C 2 ) 2 (O 2 CCF 3 ) 8 (2-pyzCONH 2 ) 3 (3) is prepared from a mixture of Ag 2 C 2 , RCO 2 Ag (R = CF 3 ) and AgBF 4 and contains a m 8 -Z 2 -C 2 unit embedded in an Ag 8 cage and a second m 6 -bound C 2 unit contained in an open arrangement of six silver atoms, one of which forms the common vertex of the infinite column structure. The triple salt Ag 20 (C 2 ) 4 (O 2 CC 2 F 5 ) 8 (2-pyzCOO) 4 -

show abstract

Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM′Re₂S₄ Cubanes (M = Ir, Rh, Ru; M′ = Pt, Pd)

Cited by 4 publications

References 62 publications

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

An Iodido‐Bridged Dimer of Cubane‐Type RuIr₃S₄ Cluster: Structural Rearrangement to New Octanuclear Core and Catalytic Reduction of Hydrazine

Organo-transition metal cluster complexes

Contact Info

Product

Resources

About

Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM′Re2S4 Cubanes (M = Ir, Rh, Ru; M′ = Pt, Pd)

Cited by 4 publications

References 62 publications

Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores

Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores

An Iodido‐Bridged Dimer of Cubane‐Type RuIr3S4 Cluster: Structural Rearrangement to New Octanuclear Core and Catalytic Reduction of Hydrazine

Organo-transition metal cluster complexes

Contact Info

Product

Resources

About

Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM′Re₂S₄ Cubanes (M = Ir, Rh, Ru; M′ = Pt, Pd)

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

Tetrametallic Thorium Compounds with Th₄E₄ (E = S, Se) Cubane Cores

An Iodido‐Bridged Dimer of Cubane‐Type RuIr₃S₄ Cluster: Structural Rearrangement to New Octanuclear Core and Catalytic Reduction of Hydrazine