Organic reactions upon dimetalated olefins. Insertion reactions at both ends of the alkyne in the dirhenium complex Re(CO)[sub 4][trans-[mu]-HC=C(CO[sub 2]Me)]Re (CO)[sub 4](NCMe)

Journal Article · Thu Mar 31 23:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00016a031· OSTI ID:7165980

Adams, R D; Chen, L; Wu, W ^[1]

---

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

The reaction of (OC)[sub 4]Re[trans-[mu]-HC=C(CO[sub 2]Me)Re(CO)[sub 4](MeCN)], 1, with CS[sub 2] yielded the new complex (OC)[sub 4]Re[(E)-HC=C(CO[sub 2]Me)CS[sub 2]]Re(CO)[sub 4], 2, in 78% yield by displacement of the NCMe ligand and the addition and insertion of a CS[sub 2] molecule into one of the Re-C bonds in 1. The CS[sub 2] grouping is chelated to the rhenium atom through the sulfur atoms. Reaction of 2 with pyridine N-oxide yielded two new compounds (OC)[sub 4]Re[OC(H)C(CO[sub 2]Me)C(S)S]Re(CO)[sub 4], 3a, in 97% yield and an isomer Re[sub 2](CO)[sub 8][[mu]-SC(S)C(CO[sub 2]Me)C(H)O], 4a, in 3% yield. The related sulfur derivatives (OC)[sub 4]Re[SC(H)C(CO[sub 2]Me)CS[sub 2]]Re(CO)[sub 4], 3b, 50% yield, and Re[sub 2](CO)[sub 8][[mu]-SC(S)C(CO[sub 2]Me)C(H)S], 4b, 6% yield, were obtained from the reaction of 2 with ethylene sulfide at 25 [degrees]C for 3 h. Compounds 3a,b will isomerize to 4a,b in quantitative yields. Compounds 3a,b were formed by the insertion of the heteroatom O or S into the Re-C bond in 2. The isomers 4a,b were formed by release of the coordinated carboxylate group in 3a,b and the formation of a bridging coordination between the rhenium atoms by one of the sulfur atoms of the CS[sub 2] grouping. 14 refs., 5 figs., 6 tabs.

• OSTI ID: 7165980
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:4; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ADDUCTS
ALKENES
ALKYNES
CARBONYLS
CHELATES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
HYDROCARBONS
INFORMATION
ISOMERIZATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RHENIUM COMPLEXES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION