There is considerable interest in MnOH x moieties, particularly in the stepwise changes in those O–H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOH x }, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pin F ) 2− including the first example of a crystallographically characterized mononuclear {Mn( iii )OH} with all O-donors, K 2 [Mn(OH)(pin F ) 2 ], 3. Complex 3 is prepared via deprotonation of K[Mn(OH 2 )(pin F ) 2 ], 1, the p K a of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large Δ E p , assigned to the Mn( iii / ii ) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O–H bond in {Mn( ii )–OH 2 } is estimated to be 67–70 kcal mol −1 . Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K 2 [Mn(OAc)(pin F ) 2 ], 2, proposed to result from the oxidation of Et 2 O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et 2 O, but addition of O 2 at low temperature effects the formation of a new chromophore proposed to be a Mn( iv ) species. The related complexes K(18C6)[Mn( iii )(pin F ) 2 ], 4, and (Me 4 N) 2 [Mn( ii )(pin F ) 2 ], 5, have also been prepared and their properties discussed in relation to complexes 1–3.
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Formation of monomeric Sn( ii ) and Sn( iv ) perfluoropinacolate complexes and their characterization by 119 Sn Mössbauer and 119 Sn NMR spectroscopies
The synthesis and characterization of a series of Sn( ii ) and Sn( iv ) complexes supported by the highly electron-withdrawing dianionic perfluoropinacolate (pin F ) ligand are reported herein. Three analogs of [Sn IV (pin F ) 3 ] 2− with NEt 3 H + ( 1 ), K + ( 2 ), and {K(18C6)} + ( 3 ) counter cations and two analogs of [Sn II (pin F ) 2 ] 2− with K + ( 4 ) and {K(15C5) 2 } + ( 5 ) counter cations were prepared and characterized by standard analytical methods, single-crystal X-ray diffraction, and 119 Sn Mössbauer and NMR spectroscopies. The six-coordinate Sn IV (pin F ) complexes display 119 Sn NMR resonances and 119 Sn Mössbauer spectra similar to SnO 2 (cassiterite). In contrast, the four-coordinate Sn II (pin F ) complexes, featuring a stereochemically-active lone pair, possess low 119 Sn NMR chemical shifts and relatively high quadrupolar splitting. Furthermore, the Sn( ii ) complexes are unreactive towards both Lewis bases (pyridine, NEt 3 ) and acids (BX 3 , Et 3 NH + ). Calculations confirm that the Sn( ii ) lone pair is localized within the 5s orbital and reveal that the Sn 5p x LUMO is energetically inaccessible, which effectively abates reactivity.
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- Award ID(s):
- 1800313
- NSF-PAR ID:
- 10294711
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 49
- Issue:
- 39
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 13773 to 13785
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0dt02837a
