Cluster Carbonyls of the [Re6(μ3-Se)8]2+Core

Orto, Peter J.; Nichol, Gary S.; Wang, Ruiyao; Zheng, Zhiping

doi:10.1021/ic700561q

Cited by 23 publications

(12 citation statements)

References 22 publications

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“…As an initial step, the reaction of [Re 6 (μ 3 -Se) 8 (PEt 3 ) 5 (CO)](SbF 6 ) 2 with CH 3 Li was carried out to synthesize the corresponding acyl complex [Re 6 (μ 3 -Se) 8 (PEt 3 ) 5 (COCH 3 )](SbF 6 ), a key intermediate, upon protonation or alkylation, to the desired cluster-carbene complexes. 30 The monoacyl complex was successfully obtained and characterized spectroscopically and crystallographically (Fig. 19).…”

Section: Synthesis and Chemistry Of Cluster Carbonylsmentioning

confidence: 99%

Chemical transformations supported by the [Re6(μ3-Se)8]2+ cluster core

Zheng

2012

Dalton Trans.

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This Perspective article discusses three interesting chemical transformations promoted by the octahedral [Re 6 (μ 3 -Se) 8 ] 2+ cluster core. These include (1) nucleophilic addition of alcohols to cluster-bound nitrile(s) to produce imino ester complexes; (2) synthesis of cluster-imine complexes with geometric specificity by reacting cluster nitrile solvates with organic azides; and (3) preparation and reactivity studies of carbonyl complexes of the cluster. We found that cluster-bound nitrile ligands were activated toward nucleophilic attack by methanol or ethanol, affording predominantly the Z-configured cluster-imino ester complexes, for which a mechanism evoking bifurcated hydrogen bonding interactions involving both the alcohol OH group and two nearest Se atoms of the cluster core was proposed. When reacted with organic azides, cluster-bound nitrile ligands were displaced and cluster-imine complexes were obtained, presumably through the formation of the corresponding cluster-azide complexes, followed by their photodecomposition. Lastly, cluster complexes featuring all-terminal carbonyl ligands were synthesized. Back-bonding interactions were verified, both experimentally and by computational studies. Their thermal and photo-stabilities were also evaluated, so was their reactivity toward methyl lithium for the eventual making of cluster-carbene catalysts. These findings, together with those by others, portend an exciting, new direction in the chemistry of solid-state type transition metal clusters.

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Section: Synthesis and Chemistry Of Cluster Carbonylsmentioning

confidence: 99%

Chemical transformations supported by the [Re6(μ3-Se)8]2+ cluster core

Zheng

2012

Dalton Trans.

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“…Se), have been prepared and characterised by X-ray diffraction. 88 The first cluster carbonyls containing the [Re 6 (m 3 -Se) 8 ] 2+ core have been synthesised, 89 while a novel rhenium(III) complex containing bis(pyrazol-1-yl)methane has been prepared and studied using X-ray crystallography and DFT calculations. 90 Theoretical studies have also been used to investigate the electronic structure and spectral properties of rhenium complexes with diarylethene-containing 1,10-phenanthroline ligands.…”

Section: Rheniummentioning

confidence: 99%

Manganese, technetium and rhenium

West¹

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This Chapter reviews the literature reported during 2007 on manganese, technetium and rhenium. The synthesis of novel compounds and complexes of these metals is reviewed and new observations and inferences are reported. Research highlights for each of the metals during the year are also given. HighlightsA rare example of a manganese tetranuclear star-shaped complex has been synthesised and characterised. 27 TcO 3 F has been prepared for the first time and found to dimerise in the solid state via fluoride bridges. 70 The first tetrazolate hexanuclear rhenium cluster complexes have been prepared and studied. 99 ManganeseA facile route to the molecular compound [Mn 3 Ti(m , containing a chiral Mn 3 Ti centre, has been reported for the first time. 1 Oxidation of a manganese(III) corrole with molecular iodine has led to the synthesis of the first compound containing a Mn IV -I bond. 2 Using structural, magnetic and theoretical studies, [Mn 2 (1,4-(Si i Pr 3 ) 2 C 8 H 4 ) 2 ] has been found to contain both high and low spin manganese(II) in two very different sites, 3 while using magnetisation measurements and multifrequency high-field EPR, the largest zero-field splitting for any individual isolated manganese(II) ion has been found in a polyoxometalate complex. 4 A large [Mn 10 Na] 4 loop-of-loops aggregate has been prepared, constructed of four [Mn 10 (m 3 -O) 2 (O 2 CMe) 13 (pd) 6 (py) 2 ] À (pdH 2 = 1,3-propanediol) loops linked through Na + ions. 5 Magnetic characterisation reveals that the Mn 10 loop has an S B 4 ground state. Without the use of a surfactant as a template, single crystalline Li 4 Mn 5 O 12 nanowires have been prepared on a large scale. 6 Icosa-and hexadeca-nuclear mixed-metal clusters in which dinuclear copper(II) complexes trap oxo-bridged [Mn III 8 Mn IV 4 O 12 ] and [Mn III 6 O 6 ] cores respectively have been prepared using quinquedentate Schiff base ligands. 7 The 2D molecular magnet K 2 [Mn(H 2 O) 2 ] 3 [Mo(CN) 7 ] 2 Á 6H 2 O has been probed by a combination of neutron diffraction studies and theoretical DFT calculations. 8 Meanwhile, mechanistic studies have been carried out on the oxidation of nitrite by a {Mn 3 O 4 } 4+ core in aqueous acidic media. 9 [Mn 3 (m-O) 4 (phen) 4 (H 2 O) 2 ] 4+ (I) quantitatively oxidises HNO 2 and NO 2 À to NO 3 À , and a rate-determining 1e, 1H + electroprotic mechanism is proposed. The new Zintl phases Ca 21 Mn 4 Bi 18 and Ca 21 Mn 4 Sb 18 have been synthesised by high temperature reactions and crystallise in the space groups C2/c and C2/m, respectively. 10 Electronic band structure calculations suggest narrow-gap semiconducting behaviour for both compounds.

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“…Spectroscopic studies on the Re-CO interactions suggest that the bonding arguments normally accepted for metal carbonyls are not applicable for these complexes. 64 Iron, ruthenium, osmium…”

Section: Manganese Technetium Rheniummentioning

confidence: 99%

Organometallic chemistry of bi- and poly-metallic complexes

King

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Cluster Carbonyls of the [Re₆(μ₃-Se)₈]²⁺Core

Cited by 23 publications

References 22 publications

Chemical transformations supported by the [Re6(μ3-Se)8]2+ cluster core

Chemical transformations supported by the [Re6(μ3-Se)8]2+ cluster core

Manganese, technetium and rhenium

Organometallic chemistry of bi- and poly-metallic complexes

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