Synthesis and reactivity of heterodinuclear iron, ruthenium, and cobalt compounds containing bridging dithiomethylene ligands. Attempted synthesis of the iron carbyne compound Cp(CO)Fe triple bond CSCH3
Part I of this dissertation involves studying the reactivity of cationic dithiocarbene complexes of iron and ruthenium toward metal carbonyl anions. The cationic terminal dithiocarbene complex (Cp(CO)(NCCH3)Fe(C(SCH3)2))PF6 reacts with Na(Co(CO)4) in THF to yield the bridging heterodinuclear -dithioalkoxymethylene compound Cp(CO)Fe( -CO)( -C(SCH3)2)Co(CO)2. An X-ray structure of this compound indicates a sulfur atom of the -methylene ligand is bonded to Co forming a three-membered metallothiocyclopropane ring. Part II of this dissertation describes attempts to synthesize the thiocarbyne compound Cp(CO)Fe triple bond CSCH3 by deprotonation of the etaS-carbene compounds Cp(CO)Fe(etaS-CHSCH3) . The etaS-carbene is obtained from the acid induced cleavage of a mercaptide group from the cyclic dithioketal Cp(CO)Fe(C(SCH3)(SCH3)H). Reactions of the etaS-carbene with the bases NaH, KSCO3, OR (R = CH3, t-butyl), NMe3, or proton sponge failed to yield Cp(CO)Fe triple bond CSCH3. Reaction of the eta2-carbene with SCH3 in the presence of CS2 lead to the formation of the previously known trithiocarbonate complex Cp(CO)Fe(S2C(SCH3)) in 49% yield.
- Research Organization:
- Iowa State Univ. of Science and Technology, Ames (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6240423
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPLEXES
ACTIVATION ENERGY
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
IRON COMPLEXES
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RUTHENIUM COMPLEXES
EXPERIMENTAL DATA
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ENERGY
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)