Complexes of the [Re63-Se)8]2+ core-containing clusters with the water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) ligand: Unexpected ligand protonation and related studies

Xiaoyan Tu, Gary S. Nichol, Ruiyao Wang, Zhiping Zheng

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Abstract

Three new complexes of the [Re63-Se)8]2+ core-containing clusters with the water-soluble trialkylphosphine ligand 1,3,5-triaza-7-phosphaadamantane (PTA), [Re63-Se)8(PEt3)5(PTA)](SbF6)2 (P5PTA, 1), [Re63-Se)8(PEt3)5(PTAH)][Re63-Se)8(PEt3)5(PTA)](SbF6)5 (2), and [Re63-Se)8(PEt3)5(PTAH)]2(HBr)(SbF6)2Br4 (3) have been prepared and structurally characterized. Unexpected protonation of the cluster-bound PTA ligand was observed when coordination of 1 with HgI2 was attempted, affording compound 2 featuring a protonated PTA ligand, PTAH. Deliberate acidification of 1 with HBr produced compound 3, and the protonation was investigated by using31P NMR spectroscopy. Crystallographic studies revealed distinct structural distortions of the ligand as a result of protonation.

Original languageEnglish (US)
Pages (from-to)6030-6038
Number of pages9
JournalJournal of the Chemical Society. Dalton Transactions
Issue number43
DOIs
StatePublished - Sep 22 2008

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Protonation
Ligands
Water
Acidification
Nuclear magnetic resonance spectroscopy
1,3,5-triaza-7-phosphaadamantane

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Complexes of the [Re6(μ3-Se)8]2+ core-containing clusters with the water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) ligand: Unexpected ligand protonation and related studies",
abstract = "Three new complexes of the [Re6(μ3-Se)8]2+ core-containing clusters with the water-soluble trialkylphosphine ligand 1,3,5-triaza-7-phosphaadamantane (PTA), [Re6(μ3-Se)8(PEt3)5(PTA)](SbF6)2 (P5PTA, 1), [Re6(μ3-Se)8(PEt3)5(PTAH)][Re6(μ3-Se)8(PEt3)5(PTA)](SbF6)5 (2), and [Re6(μ3-Se)8(PEt3)5(PTAH)]2(HBr)(SbF6)2Br4 (3) have been prepared and structurally characterized. Unexpected protonation of the cluster-bound PTA ligand was observed when coordination of 1 with HgI2 was attempted, affording compound 2 featuring a protonated PTA ligand, PTAH. Deliberate acidification of 1 with HBr produced compound 3, and the protonation was investigated by using31P NMR spectroscopy. Crystallographic studies revealed distinct structural distortions of the ligand as a result of protonation.",
author = "Xiaoyan Tu and Nichol, {Gary S.} and Ruiyao Wang and Zhiping Zheng",
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