Coordination Complexes of Molybdenum with 3,6-Di-tert-butylcatechol. Addition Products of DMSO, Pyridine N-oxide, and Triphenylarsine Oxide to the Putative [MoVIO(3,6-DBCat)2] Monomer and Self-Assembly of the Chiral [{MoVIO(3,6-DBCat)2}4] Square
(2004) In Inorganic Chemistry 43(6). p.2114-2124- Abstract
- Molybdenum complexes of 3,6-di-tert-butylcatechol have been prepared from the reaction between [Mo(CO)6] and 3,6-di-tert-butyl-1,2-benzoquinone. A putative "[MoO(3,6-DBCat)2]" monomer is assumed to form initially by reaction with trace quantities of oxygen. Condensation of the reaction mixture leads to the formation of oligomeric products, including the [{MoO(3,6-DBCat)2}4] chiral square isolated by chromatographic separation. Molybdenum centers at the corner of the square are bridged by oxo ligands centered along edges. Four-fold and inversion crystallographic symmetry gives tetramers as either or isomers, and the crystal structure consists of parallel columns of squares with the same chirality. Addition of O-Subst (O-Subst = dmso,... (More)
- Molybdenum complexes of 3,6-di-tert-butylcatechol have been prepared from the reaction between [Mo(CO)6] and 3,6-di-tert-butyl-1,2-benzoquinone. A putative "[MoO(3,6-DBCat)2]" monomer is assumed to form initially by reaction with trace quantities of oxygen. Condensation of the reaction mixture leads to the formation of oligomeric products, including the [{MoO(3,6-DBCat)2}4] chiral square isolated by chromatographic separation. Molybdenum centers at the corner of the square are bridged by oxo ligands centered along edges. Four-fold and inversion crystallographic symmetry gives tetramers as either or isomers, and the crystal structure consists of parallel columns of squares with the same chirality. Addition of O-Subst (O-Subst = dmso, pyridine N-oxide, triphenylarsine oxide) ligands to [MoO(3,6-DBCat)2] occurs selectively to give cis-[MoO(O-Subst)(3,6-DBCat)2] products. All three addition complexes are fluxional in solution. The temperature-dependent stereodymanic behavior of [MoO(dmso)(3,6-DBCat)2] has been shown to occur via a trigonal prismatic intermediate (Bailar twist) that conserves the cis disposition of oxo and dmso ligands. Electrochemical and chemical reduction reactions have been investigated for [MoO(dmso)(3,6-DBCat)2] with interest in displacement of SMe2 with formation of cis-[MoO2(3,6-DBCat)2]2-. Cyclic voltammetry shows an irreversible two-electron reduction for the complex at -0.852 V (vs Fc/Fc+). Chemical reduction using CoCp2 was observed to give a product with an electronic spectrum that is generally associated with cis-[MoO2(Cat)2]2- complexes. Structural characterization revealed that the product was [CoCp2][MoO(3,6-DBCat)2], possibly formed as the product of dmso displacement upon one-electron reduction of [MoO(dmso)(3,6-DBCat)2]. (Less)
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https://lup.lub.lu.se/record/141562
- author
- Liu, Cai-Ming ; Nordlander, Ebbe LU ; Schmeh, Derek ; Shoemaker, Richard and Pierpont, Cortlandt G
- organization
- publishing date
- 2004
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Inorganic Chemistry
- volume
- 43
- issue
- 6
- pages
- 2114 - 2124
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000220295200045
- pmid:15018535
- scopus:1642401336
- ISSN
- 1520-510X
- DOI
- 10.1021/ic0354264
- language
- English
- LU publication?
- yes
- id
- 5af4ecf1-f829-4d17-b20f-f03906908ce7 (old id 141562)
- date added to LUP
- 2016-04-01 11:33:34
- date last changed
- 2022-03-12 21:33:43
@article{5af4ecf1-f829-4d17-b20f-f03906908ce7,
abstract = {{Molybdenum complexes of 3,6-di-tert-butylcatechol have been prepared from the reaction between [Mo(CO)6] and 3,6-di-tert-butyl-1,2-benzoquinone. A putative "[MoO(3,6-DBCat)2]" monomer is assumed to form initially by reaction with trace quantities of oxygen. Condensation of the reaction mixture leads to the formation of oligomeric products, including the [{MoO(3,6-DBCat)2}4] chiral square isolated by chromatographic separation. Molybdenum centers at the corner of the square are bridged by oxo ligands centered along edges. Four-fold and inversion crystallographic symmetry gives tetramers as either or isomers, and the crystal structure consists of parallel columns of squares with the same chirality. Addition of O-Subst (O-Subst = dmso, pyridine N-oxide, triphenylarsine oxide) ligands to [MoO(3,6-DBCat)2] occurs selectively to give cis-[MoO(O-Subst)(3,6-DBCat)2] products. All three addition complexes are fluxional in solution. The temperature-dependent stereodymanic behavior of [MoO(dmso)(3,6-DBCat)2] has been shown to occur via a trigonal prismatic intermediate (Bailar twist) that conserves the cis disposition of oxo and dmso ligands. Electrochemical and chemical reduction reactions have been investigated for [MoO(dmso)(3,6-DBCat)2] with interest in displacement of SMe2 with formation of cis-[MoO2(3,6-DBCat)2]2-. Cyclic voltammetry shows an irreversible two-electron reduction for the complex at -0.852 V (vs Fc/Fc+). Chemical reduction using CoCp2 was observed to give a product with an electronic spectrum that is generally associated with cis-[MoO2(Cat)2]2- complexes. Structural characterization revealed that the product was [CoCp2][MoO(3,6-DBCat)2], possibly formed as the product of dmso displacement upon one-electron reduction of [MoO(dmso)(3,6-DBCat)2].}},
author = {{Liu, Cai-Ming and Nordlander, Ebbe and Schmeh, Derek and Shoemaker, Richard and Pierpont, Cortlandt G}},
issn = {{1520-510X}},
language = {{eng}},
number = {{6}},
pages = {{2114--2124}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Inorganic Chemistry}},
title = {{Coordination Complexes of Molybdenum with 3,6-Di-tert-butylcatechol. Addition Products of DMSO, Pyridine N-oxide, and Triphenylarsine Oxide to the Putative [MoVIO(3,6-DBCat)2] Monomer and Self-Assembly of the Chiral [{MoVIO(3,6-DBCat)2}4] Square}},
url = {{http://dx.doi.org/10.1021/ic0354264}},
doi = {{10.1021/ic0354264}},
volume = {{43}},
year = {{2004}},
}