Insertion, H/D exchange, and. sigma. -bond matathesis reactions of acetylene with Cl sub 2 ScH

Journal Article · Thu Feb 01 04:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00116a024· OSTI ID:7170683

Rappe, A K ^[1]

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1. Colorado State Univ., Fort Collins (USA)

Correlated ab initio theoretical calculations at the valence double-{zeta} plus polarization level are used to study reaction paths for the reaction of acetylene with Cl{sub 2}SCH. The paths studied are the classic insertion pathway and two {sigma}-bond metathesis pathways, one resulting in H/D exchange and the other resulting in formation of a scandium acetylide. The insertion process is calculated to have a barrier of 6.3 kcal/mol with respect to the complexed acetylene (-9.1 kcal/mol with respect to free acetylene) and to be 35.5 kcal/mol exothermic with respect to free acetylene. The direct H/D exchange reaction is calculated to have a barrier of 13.7 kcal/mol with respect to free acetylene. The acetylide-forming reaction is calculated to have a barrier of 6.2 kcal/mol with respect to free acetylene and to be 15.2 kcal/mol exothermic with respect to free acetylene. The insertion pathway is the only one calculated to proceed through a metal acetylene complex. The two {sigma}-bond metathesis pathways are each calculated to proceed through a direct interaction with the Sc-H bond.

• OSTI ID: 7170683
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:2; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETYLENE
ALKYNES
CALCULATION METHODS
CHEMICAL ACTIVATION
CHEMICAL REACTION KINETICS
CHLORIDES
CHLORINE COMPOUNDS
DATA ANALYSIS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
ISOTOPE EFFECTS
KINETICS
MATHEMATICAL MODELS
ORGANIC COMPOUNDS
REACTION KINETICS
SCANDIUM CHLORIDES
SCANDIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS