Synthesis and Characterization of {Re(CO)3}4-n{PtMe3}n(OH)4, (n = 1−3). A Set of Heterobimetallic Hydroxy Cubane Complexes

Brand, Udo; Wright, and Chris A.; Shapley, John R.

doi:10.1021/ic9906914

Cited by 4 publications

(11 citation statements)

References 27 publications

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“…In a similar fashion, addition of excess hydroquinone (3) 6 ] -(m/z 799), but on standing for 1 week, these diminished in intensity, and an intense peak due to [Re 3 (OH) 4 (CO) 9 ]was seen.…”

Section: Exchange Reactions Of 1 and 2 With Phenolsmentioning

confidence: 90%

“…A similar, slow but complete exchange of OMe groups by OPh groups was observed on addition of excess phenol to 2. The tris-phenoxy species [Re 2 (-OPh) 3 (CO) 6 ]has been prepared previously from the reaction of Re 2 (CO) 10 and phenol in the presence of Me 3 NO. 21 or from the reaction of [Re 3 (CO) 10 (-H) 4 ]with an excess of phenol.…”

Section: Exchange Reactions Of 1 and 2 With Phenolsmentioning

confidence: 99%

“…22 It is also noteworthy that there is a minor ion at m/z 955 which can be assigned to the phenoxo-substituted trinuclear complex [Re 3 (OH) 3 (OPh)(CO) 9 ] -. However, with 2,4,6-tribromophenol (ROH), the monosubstituted species [Re 2 (OH) 2 (OR)(CO) 6 ] -(m/z 905) was formed rapidly, but even in the presence of excess 2,4,6tribromophenol further substitution did not occur on standing.…”

Section: Exchange Reactions Of 1 and 2 With Phenolsmentioning

confidence: 99%

“…The formation of heterobimetallic aggregates from [Re 3 (-OH) 4 (CO) 9 ]has also been recently reported. 6 The dinuclear species [Re 2 (-OR) 3 (CO) 6 ] -(1, R = H; 2, R = OMe) have been known for some time, 7-9 and 1 has also been the subject of recent studies, which suggest that the chemistry of rhenium-carbonyl-hydroxo/aquo complexes is quite extensive. 9-11 However, to date the ligand-exchange chemistry of these complexes has received little attention, though facile alkoxide exchange and insertion reactions of terminal rhenium alkoxide complexes have been described.…”

Section: Introductionmentioning

confidence: 99%

“…9-11 However, to date the ligand-exchange chemistry of these complexes has received little attention, though facile alkoxide exchange and insertion reactions of terminal rhenium alkoxide complexes have been described. 12, 13 It was therefore of interest to investigate the chemistry of analogous exchange reactions of the triply-bridged complexes [Re 2 (-OR) 3 (CO) 6 ] -, which have, in principle, three exchangeable hydroxo or alkoxo ligands. Such exchange reactions have been briefly alluded to in the literature 7, 14 but no systematic study has been carried out.…”

Section: Introductionmentioning

confidence: 99%

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Fragmentation pathways of [Re2(μ-OR)3(CO)6]− (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry †

Jiang

Hor

Yan

et al. 2000

J. Chem. Soc., Dalton Trans.

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Graphical contents entryElectrospray mass spectrometry is found to be a powerful technique for exploring the fundamental chemistry of the dinuclear hydroxo-and alkoxo-bridged species [Re 2 (-OR) 3 (CO) 6 ] -(R = H, Me); fragmentation processes include dehydration, hydride elimination and CO loss, and exchange reactions with alcohols and phenols are also reported. AbstractThe rhenium hydroxy and methoxy carbonyl complexes [Re 2 (-OR) 3 (CO) 6 ] -(R = H, Me) have been studied by negative-ion electrospray mass spectrometry (ESMS).The complexes [Re 2 (-OR) 3 (CO) 6 ] -(R = H, OMe) undergo facile exchange reactions with protic compounds, including alcohols and phenols. With dimethylmalonate, ester hydrolysis occurs giving carboxylate-containing complexes, and with H 2 O 2 or Bu t OOH, oxidation to ReO 4occurs. The feasibility and extent of these reactions can be conveniently, rapidly, and unambiguously determined by electrospray mass spectrometry, and is dependent on the acidity and steric bulk of the protic compound. The results also suggest that the complexes can be used as versatile starting materials for the synthesis of a wide range of analogous [Re 2 (-OR) 3 (CO) 6 ]complexes by simple reaction with an excess of the appropriate alcohol. By varying the applied cone voltage, the fragmentation pathways have been investigated; the hydroxy complex undergoes dehydration followed by CO loss, whereas for the methoxy complex, -hydride elimination (and CO loss) is observed, with confirmation provided by deuterium labelling studies.Under ESMS conditions, the neutral complexes [Re 2 (-OR) 2 (-dppf)(CO) 6 ] [R = H, Me; dppf =1,1'-bis(diphenylphosphino)ferrocene] undergo substantial solvolysis and hydrolysis to give mainly mononuclear species; simple parent ions (e.g. [M + H] + )are not formed in appreciable abundance, probably due to the lack of an efficient ionisation pathway.

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Section: Exchange Reactions Of 1 and 2 With Phenolsmentioning

confidence: 90%

Section: Exchange Reactions Of 1 and 2 With Phenolsmentioning

confidence: 99%