Investigation into the formation of heteronuclear clusters of formula [{Ru6C(CO)16Ag2X}2]2− (X = Cl, Br or I)

Chisholm, Danielle M.; McIndoe, J. Scott; Bodizs, Gabriella; Ang, Wee Han; Scopelliti, Rosario; Dyson, Paul J.

doi:10.1007/s10876-007-0110-4

Cited by 7 publications

(4 citation statements)

References 47 publications

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“…Moreover, the bond angle of Cu(1)−Cl(1)−Cu(2a) is 119.4(1) o , which is much larger than that found in [{TeRu 5 (CO) 14 } 2 Cu 4 Cl 2 ] 2− (77.19(5) o ), [{Ru 6 C(CO) 16 } 2 Cu 4 Cl 2 ] 2− (86.9(2) o ), and [{Fe 4 Cu 2 C(CO) 12 (μ-Cl)} 2 ] 2− (92.18(4) o ) but closer to [{SeFe 3 (CO) 9 } 2 Cu 4 Cl 2 ] 2− (104.73(5) o ) because of the effect of nonbonded Cu···Cu. The bonding mode of the M 4 X 2 unit in 4a is similar to that in [{Ru 6 C(CO) 16 } 2 Cu 2 Ag 2 Cl 2 ] 2− and [{Ru 6 C(CO) 16 } 2 Ag 4 X 2 ] 2− (X = Cl, Br, I) , and is the same as that found in [{SeFe 3 (CO) 9 } 2 Cu 4 Cl 2 ] 2− …”

Section: Resultssupporting

confidence: 76%

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Chen

Lee

et al. 2009

Inorg. Chem.

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When the tellurium-capped tri-iron carbonyl cluster [Et(4)N](2)[TeFe(3)(CO)(9)] was treated with 1 equiv of CuX in THF at 0 degrees C, CuX-incorporated clusters [Et(4)N](2)[TeFe(3)(CO)(9)CuX] (X = Cl, [Et(4)N](2)[1a]; Br, [Et(4)N](2)[1b]; I, [Et(4)N](2)[1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe(3) core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X = Cl, Br) or 1:3 (X = I) in tetrahydrofuran (THF) or MeCN at 0 degrees C, Cu(2)X(2)-incorporated clusters [Et(4)N](2)[TeFe(3)(CO)(9)Cu(2)X(2)] (X = Cl, [Et(4)N](2)[2a]; Br, [Et(4)N](2)[2b]; I, [Et(4)N](2)[2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe(3) core, in which one TeFe(2) plane was asymmetrically bridged and capped by one mu(3)-CuCl and another mu(4)-CuCl with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu(3)X-incorporated di-TeFe(3) clusters [{TeFe(3)(CO)(9)}(2)Cu(3)X](2-) (X = Cl, 3a; Br, 3b; I, 3c), respectively, upon treatment with 1 equiv of [Cu(MeCN)(4)][BF(4)] at 0 degrees C. X-ray analysis showed that 3b and 3c each consisted of two TeFe(3) clusters that were linked by a Cu(3)X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN)(4)][BF(4)] at room temperature produced Cu(4)X(2)-linked di-TeFe(3) clusters [{TeFe(3)(CO)(9)}(2)Cu(4)X(2)](2-) (X = Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe(3) cores linked by a Cu(4)Cl(2) moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et(4)N](2)[TeFe(3)(CO)(9)] with 4 equiv of CuX (X = Cl, Br) in THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe(3) clusters are explained in terms of the effects of tellurium, copper halide, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.

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Section: Resultssupporting

confidence: 76%

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Chen

Lee

et al. 2009

Inorg. Chem.

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“…In conclusion, mass spectrometry continues to be a powerful tool to explore cluster formation and reactivity, and to direct the synthesis of novel materials. [9,12,21] Nanoclusters comprised of only a few metal atoms are particularly suitable for MS-based studies. Herein, we have shown that treatment of silver salts with sodium borohydride in the presence of a bis(phosphino) bidentate ligand yields silver hydride clusters rather than leading to the all-metallic clusters observed for related reductions of gold salts.…”

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confidence: 99%

“…Received: March 23, 2013 Published online: June 21,2013 . Keywords: cluster compounds · gas-phase reactions · mass spectrometry · silver hydride · X-ray crystallography…”

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Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄

et al. 2013

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Coinage metal hydrides continue to attract attention because of their interesting structural and physical properties, as well as for their role as reagents or intermediates in the transformation of organic substrates. For example, several copper hydride compounds have been structurally characterized and developed as catalysts for 1,4 reduction reactions of enones and for hydrocupration of alkynes. [1] In contrast, whereas their heavier congeners have been implicated as reactive intermediates in oxidation and other reactions, [2] and have been characterized in the gas phase, [3] as well as by matrix isolation experiments, [4] few silver and gold hydride compounds have been synthesized and structurally characterized by X-ray crystallography. [5] We have been examining the role of coinage-metal cluster compounds in CÀC bond coupling reactions, [6] click chemistry, [7] and C À X bond activation [3,8] of organic substrates. In our work, methods based on mass spectrometry (MS) are employed to explore cluster formation and reactivity, and to direct condensed phase synthesis and characterization of novel clusters. [9] As part of this cluster chemistry program, we became interested in extending the method of generating bis(phosphino)-protected gold nanoclusters by sodium borohydride reduction of gold salts [10] to generate related silver nanoclusters. [11] Herein, we report on the serendipitous MSbased discovery of a novel silver hydride cluster, [Ag 3 HClL 3 ] + (L = bis(phosphino) ligand), which has prompted its massspectrometry-directed synthesis [12] and X-ray and neutron crystallographic structural characterization, which reveal a {Ag 3 (m 3 -H)(m 3 -Cl)} + core structure. [13,14] The gas-phase reactivity of this cluster is also explored.Electrospray ionization mass spectrometry (ESI-MS) analysis of methanol/chloroform solutions of silver(I) trifluoroacetate [Ag I (tfa)] that had been treated with sodium borohydride in the presence of 1,1-bis(diphenylphosphino)methane (designated hereafter as L) showed evidence of the formation of silver hydride cluster cations (Figure 1; see also the Supporting Information, Figure S1), which, based on isotope patterns (Figures S2 and S3) and high resolution accurate mass measurements (Table S1), are formulated as: [Ag 3 HL 3 ] 2+ , [Ag 3 HClL 3 ] + , [Ag 3 Cl 2 L 3 ] + and [Ag 10 H 8 L 6 ] 2+ . The species [Ag 3 H 2 L 3 ] + was not observed in any of the spectra recorded. Replacing NaBH 4 with sodium borodeuteride confirmed that NaBH 4 is the source of the hydride in the clusters (for example, formation of [Ag 3 DL 3 ] 2+ and not [Ag 3 HL 3 ] 2+ ; Figures S4 and S5).The observation of abundant silver hydride cluster cations by ESI-MS encouraged us to refine the condensed-phase synthetic route (Supporting Information, Method A) to allow the isolation of a crystalline salt suitable for characterization by IR and 1 H NMR spectroscopy ( Figures S6 and S7, as well as supporting text), as well as structural determination by single-crystal X-ray diffraction and neutron diffraction. The...

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“…In conclusion, mass spectrometry continues to be a powerful tool to explore cluster formation and reactivity, and to direct the synthesis of novel materials 9. 12, 21 Nanoclusters comprised of only a few metal atoms are particularly suitable for MS‐based studies. Herein, we have shown that treatment of silver salts with sodium borohydride in the presence of a bis(phosphino) bidentate ligand yields silver hydride clusters rather than leading to the all‐metallic clusters observed for related reductions of gold salts 10.…”

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confidence: 99%

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄

et al. 2013

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Investigation into the formation of heteronuclear clusters of formula [{Ru6C(CO)16Ag2X}2]2− (X = Cl, Br or I)

Cited by 7 publications

References 47 publications

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄

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Investigation into the formation of heteronuclear clusters of formula [{Ru6C(CO)16Ag2X}2]2− (X = Cl, Br or I)

Cited by 7 publications

References 47 publications

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Copper Halide-Incorporated Tellurium−Iron Carbonyl Complexes: Transformation, Electrochemical Properties, and Theoretical Calculations

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag3{(PPh2)2CH2}3(μ3‐H)(μ3‐Cl)]BF4

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag3{(PPh2)2CH2}3(μ3‐H)(μ3‐Cl)]BF4

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Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄

Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag₃{(PPh₂)₂CH₂}₃(μ₃‐H)(μ₃‐Cl)]BF₄