Role of the metal-metal bond in transition-metal clusters. Phosphido-bridged diiron carbonyl complexes

Collman, James P.; Rothrock, Richard K.; Finke, Richard G.; Moore, Eric J.; Rose‐Munch, Françoise

doi:10.1021/ic00131a029

Cited by 88 publications

(49 citation statements)

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“…Comparable results were previously reported for the oxidation of [W 2 (l-SBz)(CO) 8 ] 2À [43] and the reduction of Fe 2 (lPPh 2 )(CO) 6 [45] which are two-electron processes leading to metal-metal bond formation and cleavage, respectively (see also [46]). For a given scan rate, the peak to peak separation for the reduction of 1 at a platinum electrode is significantly larger than that observed at a freshly polished GC electrode (Table 1).…”

Section: Resultssupporting

confidence: 85%

“…Hydrogen is further evolved from the proton-hydride reaction in the presence of excess acid. The reaction of iron(0) species with protons to give iron(II) hydrides and then hydrogen evolution has already been reported [5,45]. We also observed proton reduction in CO-saturated solutions of 2, suggesting that the loss of one CO ligand upon reduction is not a prerequisite for the formation of iron(II) hydride.…”

Section: Resultssupporting

confidence: 78%

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Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters

Capon¹,

Gloaguen²,

Schollhammer³

et al. 2004

Journal of Electroanalytical Chemistry

135

101

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Section: Resultssupporting

confidence: 85%

Section: Resultssupporting

confidence: 78%

Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters

Capon¹,

Gloaguen²,

Schollhammer³

et al. 2004

Journal of Electroanalytical Chemistry

135

101

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“…Samples of DP were prepared by using literature methods [29] and confirmed to be pure by spectroscopic and electrochemical analyses. Samples of p-toluenesulfonic acid, HOTs, (Merck) were obtained from commercial sources and used without further purification.…”

Section: Experimental Section General Remarksmentioning

confidence: 99%

XAFS and DFT Characterisation of Protonated Reduced Fe Hydrogenase Analogues and Their Implications for Electrocatalytic Proton Reduction

Cheah

Best

2011

Eur J Inorg Chem

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The relationship between the structures of reduced, protonated diiron compounds relevant to the diiron subsite of the Fe-hydrogenase H cluster, [2Fe] H , and the rate of electrocatalytic proton reduction is explored by a combination of experimental and computational approaches. Analysis of the X-ray absorption fine structure (XAFS) of the two-electron, twoproton product of [Fe(CO) 3 ] 2 (μ-PPh 2 ) 2 (DP) shows distortions of the primary coordination environment of the Fe centre that result from the trans influence of the terminally bound hydrido ligand. The difference in Fe-C(O) bond lengths for the CO groups cis and trans to the hydrido ligand is similarly predicted by density functional theory, although there is relatively poor agreement between the magnitude of the difference obtained by XAFS and DFT methods. The calculated energies of the cis and trans stereoisomers of DP-H 2 with both hydrido ligands normal to the FeP2 plane (axial:axial)

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“…The free salicylate ion shows a strong band at 1295 cm )1 which shifts to higher frequency and appears at 1308 cm )1 . Two new bands appearing at 571 and 565 cm )1 are assigned to m(Mn-O) arising from coordination of the carboxylate group of the salicylate ion [33].…”

Section: Ir Spectrummentioning

confidence: 99%

“…The behavior of the Mo complex is attributed to arise from metal-metal bond formation accompanied by structural arrangement [33]. However, from a sequential one electron oxidation of [Mn I;I 2 (CO) 6 (SPh) 3 ] ) in two steps, McDonald proposed the absence of metal-metal bonding in the complex.…”

Section: Cyclic Voltammetrymentioning

confidence: 99%

Synthesis and Crystal Structure of [Mn2(H2sal)2(Hsal)2(H2O)4]. First Example of the Reductive Synthesis of a Binuclear Manganese(I) Salicylate Complex

Lal

Lemtur

Choudhury

et al. 2006

Transition Met Chem

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The synthesis and characterization of the first unique binuclear manganese(I) salicylate complex is described. The structure of the complex is unequivocally established with the help of an X-ray crystallographic study. The structure consists of two [MnO 6 ] units, containing octahedral Mn I ions, linked together by a bridging salicylato (Hsal ) ) ligand and each Mn I is chelated with a (H 2 sal) ligand. The complex possesses a metal oxidation state of +1 and is a rare example of a noncarbonyl or cyanide complex of a binuclear Mn I species. The effective magnetic moment per binuclear molecule ( l eff: ) at 27°C is 8.07 l B; that also describes the manganese (+1) oxidation state.

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Role of the metal-metal bond in transition-metal clusters. Phosphido-bridged diiron carbonyl complexes

Cited by 88 publications

References 0 publications

Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters

Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters

XAFS and DFT Characterisation of Protonated Reduced Fe Hydrogenase Analogues and Their Implications for Electrocatalytic Proton Reduction

Synthesis and Crystal Structure of [Mn2(H2sal)2(Hsal)2(H2O)4]. First Example of the Reductive Synthesis of a Binuclear Manganese(I) Salicylate Complex

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