Nucleophilic ring opening of bridging thietanes in open triosmium cluster complexes

Journal Article · Wed Jul 01 00:00:00 EDT 1992 · Organometallics

DOI:https://doi.org/10.1021/om00043a035· OSTI ID:567342

Adams, R D; Belinski, J A ^[1]

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1. Univ. of South Carolina, Columbia, SC (United States)

The complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) and Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}] (2) were obtained from the reactions of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) with 3,3-dimethylthietane (DMT) and thietane, respectively, at -42 {degree}C in the presence of Me{sub 3}NO. Compound 1 was characterized by a single-crystal X-ray diffraction analysis and was found to contain a DMT group bridging two of the nonbonded metal atoms in the open cluster of three metal atoms by using both lone pairs of electrons on the sulfur atom. Compound 1 reacted with bis(triphenylphosphine)nitrogen(1+) chloride ([PPN]Cl) at 25 {degrees}C to yield the salt [PPN][Os{sub 3}-(CO){sub 9}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}{sub 3}-S)] (3; 76%), in which the chloride ion was added to one of the methylene groups of the DMT ring in a process that caused the ring to open by cleavage of one of the carbon-sulfur bonds. A 4-chloro-3,3-dimethylpropanethiolate ligand bridges the open edge of the anionic triosmium cluster. Compound 3 was converted to the neutral complex Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (4) by reaction with HCl at 25 {degrees}C. Compound 4 is structurally similar to 3, except that is contains a hydride ligand bridging one of the two metal-metal bonds. Compounds 1 and 2 react with HCl in CH{sub 2}Cl{sub 2} solvent to yield the neutral compounds 4 and Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (5) in 89% and 90% yields, respectively, in one step. 11 refs., 3 figs., 10 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 567342
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 7 Vol. 11; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
40 CHEMISTRY
CARBON
CHEMICAL BONDS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CLEAVAGE
DESULFURIZATION
HETEROCYCLIC COMPOUNDS
LIGANDS
MOLECULAR STRUCTURE
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
QUALITATIVE CHEMICAL ANALYSIS
STRUCTURAL CHEMICAL ANALYSIS
SULFUR
SYNTHESIS
X-RAY DIFFRACTION