2019

Inorganic Chemistry

Rocznik: 2019 | Tom: 58

artykuł naukowy

angielski

EN

We present evidence of a spin-state change that accompanies desilylation reactions performed on two related Fe(II) iminopyridine coordination complexes. To probe these systems, we performed titrations with CsF in solution and analyzed the speciation with in situ magnetometry, electrochemistry, and mass spectrometry techniques. We find that pendant tert-butyldimethylsilyl groups are readily cleaved under these conditions, and the resulting desilylated complexes exhibit overall decreased solution magnetic susceptibility values. Density functional theory and ab initio computations probe the impact of substituent identity (prior to- and post-desilylation) on the metal-ligand σ-donor and -acceptor bonding properties. We attribute the observed spin-state changes to the decrease in entropy associated with the conformational freedom of the silylated high-spin complex, resulting in a more favored low-spin state upon desilylation.

7785 - 7793

10.1021/acs.inorgchem.9b00340

http://150.254.65.57/info/article/UAM4146801ccb09483f8087dba8254f0069/

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