Studies of the insertion of an organic isothiocyanate into a rhenium-rhenium single bond and a new mode of metal-promoted coupling of isothiocyanates

Journal Article · Tue Aug 20 04:00:00 EDT 1996 · Organometallics

DOI:https://doi.org/10.1021/om950675o· OSTI ID:374506

Adams, R D; Huang, M ^[1]

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

Recently, we have shown that carboxylate-substituted alkynes undergo facile insertion into the metal-metal bonds of activated dimanganese and dirhenium complexes to yield dimetalated olefin complexes. We have now found that EtO{sub 2}CN=C=S undergoes a facile insertion into the rhenium-rhenium bond in Re{sub 2}(CO){sub 9}(NCMe) (1) to yield dimetalated thioimidate complexes [e.g., Re(CO){sub 4} [s-trans-{mu}-C,S-EtO{sub 2}CN=CS]Re(CO){sub 5} (2)]. We have also observed products formed by a new coupling/rearrangement process involving two isothiocyanate molecules. Details of this study are reported here. Our results demonstrate that the insertion of small molecules into the Re-Re bond of dirhenium carbonyl complexes is more general than we originally observed and can lead to a variety of new metalated ligand complexes that can be transformed still further. The reactions of other dinuclear metal complexes with M-M single bonds can be anticipated to proceed similarly. Also, it seems likely that dimetalated thioimidate complexes should be susceptible to reaction with other small molecules and lead to other new ligands and new organic molecules. 14 refs., 10 figs., 1 tab.

• OSTI ID: 374506
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 17 Vol. 15; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTIONS
CRYSTALLOGRAPHY
CYANATES
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RHENIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
X-RAY DIFFRACTION