Synthesis and structure of the new cubane-like cluster [Fe4Te4(PEt3)4]PF6, containing only terminal phosphine ligands

Cecconi, Franco; Ghilardi, Carlo A.; Midollini, Stefano; Orlandini, Annabella

doi:10.1039/c39920000910

Cited by 7 publications

(3 citation statements)

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“…To the best of our knowledge, this is the first instance of a hexanuclear core copper(I) carboxylate. Among other copper(I) compounds, examples are limited to [{MeC(CH 2 PPh 2 ) 3 }CoP 3 ] 2 (CuBr) 6 ‚CH 2 Cl 2 , which has six copper atoms bridged by bromide ligands, 18 and the phosphido-bridged [Cu 12 (PPh) 6 (PPh 3 ) 6 ] compound. The latter is built of three interpenetrated planar [Cu 6 ] units that form a Cu 12 cuboctahedron.…”

Section: Resultsmentioning

confidence: 99%

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

2007

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The carboxylate ligand-exchange reaction of copper(I) trifluoroacetate by 3,5-difluorobenzoate yielded a new product, [Cu(O2C(3,5-F)2C6H3)] (1). Single crystals of 1 suitable for X-ray structural characterization were obtained by sublimation-deposition procedures at 230 degrees C. An X-ray diffraction study revealed a remarkable planar hexanuclear copper(I) core supported by bridging carboxylates, the first such structural type among other known copper(I) carboxylates. The Cu...Cu distances within the core range from 2.7064(8) to 2.8259(8) A and fall into the category of cuprophillic interactions. The hexacopper unit remains intact upon gas-phase deposition with a planar polyarene, coronene (C24H12), to give [Cu6(O2C(3,5-F)2C6H3)6](C24H12) (2). Density functional theory calculations suggest the latter compound to be a cocrystallization product having electrostatic interactions between the hexacopper complex and coronene. However, cocrystallization affects the photophysical properties of 2. While copper(I) 3,5-difluorobenzoate (1) exhibits photoluminescence at ca. 554 nm (lambda(ex) = 350 nm) in the solid state, compound 2 is nonluminescent at room temperature in the visible region. Gas-phase and solution reactions of 1 with alkyne ligands, diphenylacetylene (C14H10) and 1,4-bis(p-tolylethynyl)benzene (C24H18), result in the rupture of the [Cu6] core to afford dinuclear organometallic copper(I) complexes. The latter have a dimetal core cis-bridged by two carboxylate groups with acetylene ligands eta(2)-coordinated to each copper(I) center.

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Section: Resultsmentioning

confidence: 99%

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

2007

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“…In this context, we note the stable compounds [Fe 4 Te 4 (PEt 3 ) 4 ] 1+,0 . ,, The mean Fe−P bond lengths of [Fe 4 Te 4 (PR 3 ) 4 ] correlate with cone angle: R = Et (2.390(6) Å) < Pr i (2.447(6) Å),31b as in the series [Fe 4 S 4 (PR 3 ) 4 ] 1+ above.…”

Section: Referencesmentioning

confidence: 93%

“…Calcd for C96H152BFe4P4S4: C, 64. 32;H,8.55;B,0.60;Fe,12.46;P,6.91;S,7.15. Found: C,64.28;H,8.43;B,0.57;Fe,12.58;P,7.08;S,7.14.…”

Section: Methodsmentioning

confidence: 99%

Polycubane Clusters: Synthesis of [Fe₄S₄(PR₃)₄]^1+,0 (R = Bu^t, Cy, Prⁱ) and [Fe₄S₄]⁰ Core Aggregation upon Loss of Phosphine

et al. 1996

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The influence of tertiary phosphines on the stability of FeS3P coordination units and the formation of iron−sulfur clusters has been investigated. Reaction of [Fe4S4Cl4]2- with a small excess of PR3 in acetonitrile/THF affords the cubane-type clusters [Fe4S4(PR3)4]1+ (R = Cy, But, Pri), one-electron reduced over the initial cluster and possessing an S = 1/2 ground state. These clusters may be electrochemically oxidized to [Fe4S4(PR3)4]2+ and reduced to [Fe4S4(PR3)4], which can also be generated in solution by chemical reduction. The neutral clusters upon standing in solution lose phosphine and aggregate to form dicubane ([Fe8S8(PCy3)6]) or tetracubane ([Fe16S16(PR3)8]; R = But, Pri) clusters. The [Fe8S8]0 dicubane core has two intercubane Fe−S bonds, defining an Fe2S2 rhomb and affording a structure of overall idealized C 2h symmetry. The tetracubane clusters consist of a cyclic array of four cubanes joined in four Fe2S2 rhombs in a structure of overall D 4 symmetry, and present a new structural motif in Fe−S cluster chemistry. Tertiary phosphines impose two significant features on this cluster chemistry. These ligands significantly stabilize the [Fe4S4]1+/0 core oxidation levels compared to the case of conventional [Fe4S4L4]3-,4- clusters (L = monoanion). Ligands with cone angles exceeding that of PEt3 (132°) favor tetrahedral FeS3P coordination sites. This has the effect of directing reactions away from the formation of Fe6S6 (four trigonal pyramidal) and Fe6S8 (six square pyramidal) clusters having the indicated sites which are disfavored by large cone angles. Structural principles governing polycubane clusters together with a brief enumeration of stereochemically feasible polycubanes are presented and discussed.

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Synthesis, Structure, and Electrical Properties of Ta₄FeTe₄

1995

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Ta,FeTe, has been synthesized and its structure determined by single-crystal X-ray methods. It crystallizes in the orthorhombic space group Pbam wi !h Z = 4 and a = 10.514(5), b = 18.2?5(?), and c = 4.815(1) A. Ta4FeTe, has a chain structure built up by Fe-centered Ta8-square antiprisms sharing common square faces. The resistivity of Ta4FeTe4 has been measured by a two-point method. Ta,FeTe, shows metallic behavior. The structure of Ta4FeTe4 is discussed in relation to other early transition metal cluster compounds. A rational approach to the synthesis of related compounds is proposed.

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Synthesis and structure of the new cubane-like cluster [Fe4Te4(PEt3)4]PF6, containing only terminal phosphine ligands

Cited by 7 publications

References 5 publications

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

Polycubane Clusters: Synthesis of [Fe₄S₄(PR₃)₄]^1+,0 (R = Bu^t, Cy, Prⁱ) and [Fe₄S₄]⁰ Core Aggregation upon Loss of Phosphine

Synthesis, Structure, and Electrical Properties of Ta₄FeTe₄

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Synthesis and structure of the new cubane-like cluster [Fe4Te4(PEt3)4]PF6, containing only terminal phosphine ligands

Cited by 7 publications

References 5 publications

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

The First Hexanuclear Copper(I) Carboxylate: X-ray Crystal Structure and Reactivity in Solution and Gas-Phase Reactions

Polycubane Clusters: Synthesis of [Fe4S4(PR3)4]1+,0 (R = But, Cy, Pri) and [Fe4S4]0 Core Aggregation upon Loss of Phosphine

Synthesis, Structure, and Electrical Properties of Ta4FeTe4

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Polycubane Clusters: Synthesis of [Fe₄S₄(PR₃)₄]^1+,0 (R = Bu^t, Cy, Prⁱ) and [Fe₄S₄]⁰ Core Aggregation upon Loss of Phosphine

Synthesis, Structure, and Electrical Properties of Ta₄FeTe₄