Isomeric complexes of platinum, which contain two non-innocent ligands are reported. The built-in coordination asymmetry in the ligands makes it possible to separate two different positional isomers. Results from X-ray crystallography is used to invoke the popular structure oxidation state correlation in these complexes. The redox processes are discussed and interpreted with the help of UV-vis-NIR and EPR spectroelectrochemistry.
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http://dx.doi.org/10.1039/b902645b | DOI Listing |
RSC Adv
November 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Berhampur Transit Campus, (Govt. ITI Building), Engineering School Junction Berhampur 760010 Odisha India
The ambiguous nature of non-innocent ligand catalysts provides an excellent strategy for developing an efficient catalyst system featuring extended applicability in sustainable catalysis. In this study, we unveil the catalytic activity of an NNN-Ru catalyst for lactic acid synthesis from a mixture of glycerol, ethylene glycol, and methanol. The developed strategy was also implemented to synthesize lactate (up to 80% yield) with good selectivity the dehydrogenative upgradation of a crude glycerol and ethylene glycol mixture.
View Article and Find Full Text PDFDalton Trans
October 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, West Bengal, India.
Chem Sci
September 2024
Laboratory of Inorganic Chemistry (LAC), Department of Chemistry and Applied Biosciences (D-CHAB), ETH Zurich Vladimir-Prelog Weg 2 8093 Zurich Switzerland
The investigation of fundamental properties of low-valent molybdenum complexes bearing anionic ligands is crucial for elucidating the molybdenum's role in critical enzymatic systems involved in the transformation of small molecules, including the nitrogenase's iron molybdenum cofactor, FeMoco. The β-diketonate ligands in [Mo(acac)] (acac = acetylacetonate), one of the earliest low-valent Mo complexes reported, provide a robust anionic platform to stabilize Mo in its +III oxidation state. This complex played a key role in demonstrating the potential of low-valent molybdenum for small molecule activation, serving as the starting material for the preparation of the first reported molybdenum dinitrogen complex.
View Article and Find Full Text PDFChem Sci
September 2024
Department of Chemistry, Indian Institute of Technology Madras Chennai 600036 India
In an effort to investigate small molecule activation by heavier transition metal (TM) based κ-,-chelated species, we have synthesised a series of bis-κ-1,3-,-chelated complexes of osmium, [Os(PPh)(κ-,-L/L)], 2a-b, and [Os(PPh)(L/L)(κ-,-L/L)], 3a-b (2a and 3a: L[double bond, length as m-dash] = CHNS; 2b and 3b: L = CHNS), from the thermolysis of [Os(PPh)Cl], 1, with a potassium salt of heterocyclic ligands L and L. The former complexes are diamagnetic in nature, while the EPR spectra, XPS study and density functional theory (DFT) calculations have substantiated the paramagnetic behaviour of 3a-b with a significant spin contribution from non-innocent ligands. These species were engaged in B-H activation of boranes utilizing the combined effect of hemilability and metal-ligand cooperativity (MLC), where 2a-b upon treatment with BH·SMe yielded Os(σ-borate)hydride complexes, [Os(PPh)(H){κ-,,'-BH(L/L)}], 4a-b (4a: L = CHNS; 4b: L = CHNS).
View Article and Find Full Text PDFJ Inorg Biochem
November 2024
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747, AG, Groningen, the Netherlands. Electronic address:
Redox non-innocent ligands hold the potential to expand the redox chemistry and activity of transition metal catalysts. The impact of the additional redox chemistry of phenol ligands in oxidation catalysis is explored here in the complex μ-oxido-diiron(III) polypyridyl (1) [(L)Fe(III)(μ-O)Fe(III)(L)](ClO) (where HL is 2-(((di(pyridin-2-yl)methyl) (pyridin-2-ylmethyl) amino)methyl)phenol) and its tert-butyl substituted analog 2, in which each of the Fe(III) centers is coordinated to a phenolato moiety of the ligand. Complex 1 was shown earlier to catalyse the oxidation of benzyl alcohols to aldehydes with HO.
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