Reversible Opening of a Trinuclear Heterometal Cluster

Hüttner, Gottfried; Schneider, Josef; Müller, Henrik Høeg; Mohr, G.; Seyerl, J. Von; Wohlfahrt, Lidwina

doi:10.1002/anie.197900761

Cited by 59 publications

(25 citation statements)

References 12 publications

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“…It is worthwhile to compare and contrast the structure of 2 with that of the isoelectronic tetraosmium compound Os 4 (CO) 12 (μ 3 -AuPPh 3 ) 2 , 8. 23 Compound 8 contains a butterfly cluster of four osmium atoms, but differs from 2 in that it contains twelve linear terminal carbonyl ligands, three on each osmium atom.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

2012

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The new iridium−gold complex Ir 4 (CO) 11 (Ph)(μ-AuPPh 3 ), 1 was obtained from the reaction of the tetrairidium anion [Ir 4 (CO) 11 (Ph)] − with [Au(PPh 3 )] [NO 3 ]. Two new iridium−gold complexes Ir 4 (CO) 10 (AuPPh 3 ) 2 , 2, and Ir 4 (CO) 11 (AuPPh 3 ) 2 , 3, were obtained from the reaction of [HIr 4 (CO) 11 ] − with [Au(PPh 3 )][NO 3 ]. Compounds 1−3 were structurally characterized by single crystal X-ray diffraction analyses. Compound 2 adds CO reversibly to form compound 3. In this process, the octahedral Ir 4 Au 2 cluster of 2 is converted into the Au(PPh 3 )-capped Ir 4 Au trigonal bipyramidal cluster found in 3. Compounds 2 and 3 have been investigated by DFT computational analyses in order to understand the metal−metal bonding and the mechanism of their interconversion by CO addition and elimination. Compound 2 adds PPh 3 to form the compound Ir 4 (CO) 10 (PPh 3 )-(AuPPh 3 ) 2 , 4, which is structurally similar to 3. Compound 4 loses CO and benzene when heated to form the compound Ir 4 (CO) 9 (μ 3 -PPhC 6 H 4 )(AuPPh 3 ) 2 , 5, which contains a triply bridging PPhC 6 H 4 ligand. ■ INTRODUCTIONApplications for iridium in catalysis continue to grow. 1 Although most catalytic applications are of a homogeneous type, 2 it has been shown that iridium clusters can serve as precursors to heterogeneous nanoscale catalysts that exhibit good activity for the hydrogenation of aromatics and olefins. 3 Years ago, Sinfelt showed that the addition of iridium to platinum greatly improved its activity for the catalytic reforming of petroleum. 4 Heterogeneous iridium−iron catalysts derived from bimetallic cluster complexes have been shown to exhibit exceptional catalytic activity for the formation of methanol from synthesis gas. 5 Recently, gold nanoparticles have been shown to exhibit significant catalytic activity for the oxidation of CO and certain olefins. 6 Combining transition metals with gold has led to interesting new bimetallic catalysts for the oxidation of hydrocarbons. 7 There have been very few reports of iridium−gold carbonyl cluster complexes, 8,9 and their catalytic activity has not yet been investigated.We have recently reported the synthesis and structural characterization of the tetrairidium anion, [Ir 4 (CO) 11 (Ph)] − . 10 [Ir 4 (CO) 11 (Ph)] − has been shown to react with Ir(CO)-(PPh 3 ) 2 Cl to form the pentairidium complex Ir 5 (CO) 12 Ph-(PPh 3 ) by halide displacement combined with the elimination of one PPh 3 ligand, Scheme 1. 10 It also reacts with [(COD)-Ir(Cl)] 2 to form a series of higher nuclearity iridium carbonyl cluster complexes containing COD and COD transformed ligands, Scheme 2. 11 We have now investigated the reaction of [Ir 4 (CO) 11 (Ph)] − with [Au(PPh 3 )][NO 3 ] and have obtained the gold− tetrairidium cluster complex Ir 4 (CO) 11 (Ph)(μ-AuPPh 3 ), 1. For comparisons, we have investigated the reaction of [HIr 4 -(CO) 11 ] − with [Au(PPh 3 )][NO 3 ] and have obtained two new iridium−gold carbonyl cluster complexes Ir 4 (CO) 10 (AuPPh 3 ) 2 , 2, and Ir 4 (CO) 11 (AuPPh 3 ) 2 ...

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…Mass spectrometric (MS) measurements performed by a direct-exposure probe using electron impact ionization (EI) or by electrospray ionization (ESI) were made on a VG 70S instrument. Ir 4 (CO) 12 11 Ph] (9.6 mg, 0.0075 mmol) was dissolved in 15 mL of CH 2 Cl 2 .…”

Section: ■ Introductionmentioning

confidence: 99%

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

2012

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“…CF, (5e)l. Using the same reaction conditions as for the substitution reactions described earlier these insertion products are formed in good to near quantitative yield based on complex (1) consumed (Table 1). Conversion factors are, however, low, typically 3-20% for both the thermal and photolytic reactions.…”

Section: [Mn2(p-h)(p-pph2)(co)6lz] [Lmentioning

confidence: 99%

Substitution and insertion reactions of the dinuclear manganese µ-hydride complex [M₂(µ-H)(µ-PPh₂)(CO)₈]; crystal structures of the complexes [Mn₂(µ-σ:η²-CHCH₂)(µ-PPh₂)(CO)₇] and [Mn₂(µ-H)(µ-PPh₂)(CO)₆(CNBu^t)₂]

Iggo¹,

Mays²,

Raithby³

et al. 1983

J. Chem. Soc., Dalton Trans.

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Mn2(p-H)(p-PPh2)(C0)8] (1 ) has been synthesised in 80% yield from [Mn2(CO)10] and PHPh,. Reaction of (1) with RCN, RNC, PPh3, P(OMe)3, or (EtO),POP(OEt), gives substitution products of general formulae [Mn,(p-H)(p-PPh2)(C0)7L] [L = NCMe (2a) ; NCPh (2b) ; CNBu' (2c) ; CNCH2Ph (2d) ; PPh3 (2e) ; P(OMe), (2f) ; P(OEt), (2g)], [Mn,(p-H)(p-PPh,)(CO),L,] [L = CNBu' (3a) ; L2 = (EtO),POP(OEt), (3b)], and [Mn,(p-H)(p-PPh,) (CO),{(EtO)2POP(OEt)2}2] (4). Reaction of

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“…Carbonyl complexes that incorporate two or more metal centers are particularly attractive because of their ability to provide access to catalytic reaction pathways that might not be offered in mononuclear chemistry [25][26][27][28][29][30], such as reversible metal-metal bond cleavage, skeletal rearrangement without degradation and ligand activation via multisite coordination [31][32][33][34][35][36][37].…”

Section: Introductionmentioning

confidence: 99%

High variety of coordination modes of π-conjugated phospholes in dinuclear rhenium carbonyls. Fluxional behavior of σ,π-complexes

Otero

Arce

Lescop

et al. 2019

Inorganica Chimica Acta

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A variety of dirhenium carbonyl complexes containing π-conjugated phosphole derivatives were obtained from reaction of [Re 2 (CO) 8 (CH 3 CN) 2 ] with each of the following phospholes: 2,5-bis(2-thienyl)-1-phenylphosphole (btpp), 2,5-bis(2-pyridyl)-1phenylphosphole (bpypp) and 1,2,5-triphenylphosphole (tpp). The π-conjugated phospholes were found to behave as two-, four-or six-electron donor ligands via σ or σ-π interactions with the metal centers, presenting bridging or chelating coordination modes as determined by spectroscopic methods and single crystal X-ray diffraction analysis. Metal-metal bond cleavage was evidenced when btpp was used, leading to a mono-substituted mononuclear complex. Variable-temperature 1 H NMR studies for σ,π-complexes showed a fluxional behavior due to the restricted rotation around the P-C and C-C bonds of the 1,2,5trisubstituted phosphole ring.

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Reversible Opening of a Trinuclear Heterometal Cluster

Abstract: The mode of action of metal clusters in homogeneous catalysis is hardly known. The first proof that clusters can reversibly add substrates (LCO, PPh3) via opening of metal‐metal bonds has now been obtained.

Cited by 59 publications

References 12 publications

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

Substitution and insertion reactions of the dinuclear manganese µ-hydride complex [M₂(µ-H)(µ-PPh₂)(CO)₈]; crystal structures of the complexes [Mn₂(µ-σ:η²-CHCH₂)(µ-PPh₂)(CO)₇] and [Mn₂(µ-H)(µ-PPh₂)(CO)₆(CNBu^t)₂]

High variety of coordination modes of π-conjugated phospholes in dinuclear rhenium carbonyls. Fluxional behavior of σ,π-complexes

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Reversible Opening of a Trinuclear Heterometal Cluster

Abstract: The mode of action of metal clusters in homogeneous catalysis is hardly known. The first proof that clusters can reversibly add substrates (LCO, PPh3) via opening of metal‐metal bonds has now been obtained.

Cited by 59 publications

References 12 publications

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

Substitution and insertion reactions of the dinuclear manganese µ-hydride complex [M2(µ-H)(µ-PPh2)(CO)8]; crystal structures of the complexes [Mn2(µ-σ:η2-CHCH2)(µ-PPh2)(CO)7] and [Mn2(µ-H)(µ-PPh2)(CO)6(CNBut)2]

High variety of coordination modes of π-conjugated phospholes in dinuclear rhenium carbonyls. Fluxional behavior of σ,π-complexes

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Substitution and insertion reactions of the dinuclear manganese µ-hydride complex [M₂(µ-H)(µ-PPh₂)(CO)₈]; crystal structures of the complexes [Mn₂(µ-σ:η²-CHCH₂)(µ-PPh₂)(CO)₇] and [Mn₂(µ-H)(µ-PPh₂)(CO)₆(CNBu^t)₂]