How innocent is thallium(i)? Corrected formulations of [Tl2Pd14(CO)9(PMe3)11][PF6]2 and [TlPd9(CO)9(PPh3)6][PF6] clusters previously reported as corresponding Au2Pd14 and AuPd9 clusters

Mednikov, Evgueni G.; Dahl, Lawrence F.

doi:10.1039/c2cc37959g

Cited by 8 publications

(1 citation statement)

References 23 publications

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“…Realistically, however, computationally stable results of least-squares structural refinement may not produce a chemically reasonable model or may produce a chemically reasonable but incorrect model (Mednikov & Dahl, 2013). Realistically, however, computationally stable results of least-squares structural refinement may not produce a chemically reasonable model or may produce a chemically reasonable but incorrect model (Mednikov & Dahl, 2013).…”

Section: Introductionmentioning

confidence: 99%

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Guzei

Miles

2016

Acta Crystallogr C

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The crystal structure and absolute configuration of a molecular host/guest/impurity inclusion complex were established unequivocally in spite of our having no prior knowledge of its chemical composition. The host (4R,5R)-4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane, (I), displays expected conformational features. The crystal-disordered chiral guest 4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (II), is present in the crystal 85.1 (4)% of the time. It shares a common site with 4a-hydroperoxymethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one, (III), present 14.9 (4)% of the time, which is the product of autoxidation of (II). This minor peroxide impurity was isolated, and the results of nuclear magnetic resonance, mass spectrometry, and X-ray fluorescence studies are consistent with the proposed structure of (III). The complete structure was therefore determined to be (4R,5R)-4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-dioxolane-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one-4a-hydroperoxymethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one (1/0.85/0.15), C31H30O4·0.85C10H14O·0.15C10H14O3, (IV). There are host-host, host-guest, and host-impurity hydrogen-bonding interactions of types S and D in the solid state. We believe that the crystals of (IV) were originally prepared to establish the chirality of the guest (II) by means of X-ray diffraction analysis of host/guest crystals obtained in the course of chiral resolution during cocrystallization of (II) with (I). In spite of the absence of `heavy' elements, the absolute configurations of all anomeric centres in the structure are assigned as R based on resonant scattering effects.

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Section: Introductionmentioning

confidence: 99%

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Guzei

Miles

2016

Acta Crystallogr C

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Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

Mednikov

Dahl

2013

Angewandte Chemie

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Dedicated to Professor Mike MingosDuring the last 10-15 years, bimetallic gold-palladium nanosized clusters have attracted considerable attention owing to their greater stabilities [1a] and enhanced catalytic performances compared to their single-metal counterparts. [1b,c] Likewise, a recent report [1d] revealed that bimetallic Ag-Pd nanoparticles had higher catalytic activity and selectivity for oxidation of propene to propene oxide with molecular oxygen (in methanol) than did Pd salts and Pd and Ag monometallic nanoparticles. However, syntheses of stoichiometrically defined nanosized bimetallic palladium composites with Group 11 coinage-metal elements still remain challenging: [2a] there have been no previous publications of nanosized Ag-Pd clusters. [2b] Recently we reported the synthesis of the bicuboctahedral Au-Pd Au 2 Pd 28 (CO) 26 (PEt 3 ) 10 , [2c] which, unlike its structurally analogous non-isovalent homopalladium Pd 30 cluster, was obtained under CO atmosphere by reactions of coordinatively unsaturated Pd n (CO) x (PR 3 ) y species (resulting from CO-induced fragmentations of either of two structurally dissimilar homopalladium Pd n clusters, n = 23, 38) with the CO-tolerant Au-centered cuboctahedral cluster precursor, Au 2 Pd 21 (CO) 20 (PEt 3 ) 10 . Based upon both direct crystallographic evidence and DFT calculations, [2c] the higher stability to CO of the Au 2 Pd 28 cluster was attributed to electron delocalization of each Au 6s valence electron for the two adjacent interior Au atoms instead of the formation of a localized electron-pair AuÀAu bond. This important stereochemical implication has particular relevance to the recent report [1e] that the presence of Au in Au-Pd nanoparticle catalysts, used for the complete conversion of formic acid into high-purity hydrogen (and CO 2 ) for chemical hydrogen storage, suppresses CO poisoning, in sharp contrast to early deactivation of the corresponding Pd counterpart material by carbon monoxide.Herein we present a different synthetic approach to obtain a gold-encapsulated nanosized Au-Pd cluster; appli-cation of this method is also shown to provide preparation of the first corresponding high-nuclearity Ag-Pd cluster. The resulting two remarkable isostructural nanosized M-centered cluster monocations, [(m 14 -M)Pd 22 (CO) 20 (PEt 3 ) 8 ] + , M= Au (1), Ag (2), with [(CF 3 CO 2 ) 2 H] À counterions, were obtained by two-step/one-pot reactions of Pd 10 (CO) 12 (PEt 3 ) 6 with CF 3 CO 2 H (in acetone at 50 8C) followed by coinage-metal ion exchange of protons by the addition of either Au(SMe 2 )Cl (45-60 % yields) or Ag(CF 3 SO 3 ) (28 % yield), respectively. A similar attempt to isolate the Cu-Pd analogue by incorporation of Cu + metal ion was unsuccessful. This preparative method outlined in the reaction sequence (1) is based upon: a) prior treatment of the homopalladium precursor, Pd 10 (CO) 12 (PEt 3 ) 6 (4), with CF 3 CO 2 H acid in the presence of Me 3 NO that affords a non-isolated protonated species (for example, monoprotonated [HPd n (CO) x (...

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Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

Mednikov

Dahl

2013

Angew Chem Int Ed

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Heart of gold (or silver): The pseudo-D2d distorted MPd14 cubic kernel of [(μ14-M)Pd22(CO)20(PEt3)8](+) cations, with M = Au (1), Ag (2), has an encapsulated M atom (see picture; yellow) coordinated to eight cubic corner (black) and six face-capping Pd atoms (gray). Compounds 1 and 2 were obtained (28-60 % yields) from two-step/one-pot reactions of a Pd10 precursor with CF3CO2 H followed by coinage-metal ion exchange of protons.

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How innocent is thallium(i)? Corrected formulations of [Tl2Pd14(CO)9(PMe3)11][PF6]2 and [TlPd9(CO)9(PPh3)6][PF6] clusters previously reported as corresponding Au2Pd14 and AuPd9 clusters

Cited by 8 publications

References 23 publications

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

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How innocent is thallium(i)? Corrected formulations of [Tl2Pd14(CO)9(PMe3)11][PF6]2 and [TlPd9(CO)9(PPh3)6][PF6] clusters previously reported as corresponding Au2Pd14 and AuPd9 clusters

Cited by 8 publications

References 23 publications

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Ab initioX-ray structural characterization of an inclusion compound with a compositionally disordered chiral guest: no prior knowledge of the crystal composition

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D2d Distorted Face‐Capped Pd14 Cubic Kernel: [(μ14‐M)Pd22(CO)20(PEt3)8]+ (M=Au, Ag)

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D2d Distorted Face‐Capped Pd14 Cubic Kernel: [(μ14‐M)Pd22(CO)20(PEt3)8]+ (M=Au, Ag)

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Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)