The chemistry of carbonyl clusters of transition metals containing labile and hemilabile ligands. Synthesis, reactivity, and prospects for application

Tunik, Sergey P.

doi:10.1007/s11172-005-0172-0

Cited by 6 publications

(1 citation statement)

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“…The general procedures for preparing cluster carbonyls primarily consist of pyrolysis of carbonyls of lower nuclearity, reduction of lower nuclearity carbonyls, addition of another vertex to a preexisting pentanuclear cluster ("capping"), or controlled coupling of cluster carbonyl precursors through linking ligands. 31,32 In the present study, the synthesis involves treating appropriate iodo precursors of the [Re 6 (l 3 -Se) 8 ] 2+ core-containing clusters with AgSbF 6 in the presence of CO. Facile precipitation of AgI drives the reaction forward to free the Re(III) site, and allow coordination of CO, the only appropriate ligand present in CO-saturated CH 2 Cl 2 . Precedents are available for the present synthetic approach, specifically, in the previously reported highyield syntheses of cluster solvates, wherein a silver salt, AgSbF 6 or AgBF 4 , is added to solutions of the iodo precursors with CH 3 CN, DMSO, and DMF present to act as ligands once the halide is removed via precipitation.…”

Section: Resultsmentioning

confidence: 99%

Cluster carbonyls of the [Re6(μ3-Se)8]2+ core: synthesis, structural characterization, and computational analysis

et al. 2008

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The reactions of the previously reported cluster complexes [Re(6)(mu(3)-Se)(8)(PEt(3))(5)I]I, trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)], and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)] with the [Re(6)(mu(3)-Se)(8)](2+) core with CO in the presence of AgSbF(6) afforded the corresponding cluster carbonyls [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CO)][SbF(6)](2) (), trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (), and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between and indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.

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Section: Resultsmentioning

confidence: 99%