109801-95-8

Upstream product

• 74-85-1 ethene 
• 109-67-1 1-penten 
• 14067-02-8 iron ⁽¹⁺⁾ 
• 187737-37-7 propene 
• 93604-57-0 C⁽²⁾H₂Fe⁽¹⁺⁾ 
• 12434-84-3 ⁽⁵⁶⁾FeO⁽¹⁺⁾ 
• 90143-30-9 Fe(CH₂)⁽¹⁺⁾ 

Downstream Products

• 7647-01-0 hydrogenchloride 
• 14067-02-8 ⁽⁵⁶⁾Fe⁽¹⁺⁾ 
• 129871-75-6 ferraoxacyclobutane⁽¹⁺⁾ 
• 75-07-0 acetaldehyde 

Relevant academic research and scientific papers

Reactions of FeCH2(1+) and CoCH2(1+) with Olefins in the Gas Phase. Studies Involving Olefin Metathesis

Reactions of the title carbenes with several olefins and alkynes are reported.Ethene reacts with MCH2(1+) yielding exclusively M(1+) formation (C3H6 elimination).Reaction of ethene with MCD2(1+) yields the metathesis products FeCH2(1+) and CoCH2(1+) in 20percent and 2percent yields, respectively.Formation of the metathesis product MC2H4(1+) dominates for propene with no MCH2(1+) produced from MCD2(1+).Formation of MC2H4(1+) is believed to proceed through an ethene-ethylidene intermediate that rearranges to a bis(ethene) complex followed by elimination of ethene.Absence of MCH2(1+) formation from reaction of MCD2(1+) with propene suggests that the alkene-alkylidene conversion is the key step in metathesis of olefins larger than ethene.Several other pathways compete with metathesis such as cyclopropanation, olefin homologation, dehydrogenation, and various C-C bond cleavages.Both carbenes react with butadiene, generating M-c-C5H6(1+) and M-c-C5H5(1+), implying D0(Co(1+)-C5H5) > 76+/- 7 kcal/mol and D0(Fe(1+)-C5H5) > 87 +/- 5 kcal/mol.Finally, ethyne and propyne react with MCH2(1+) to yield M(1+) as the only product.

Product Kinetic Energy Release Distributions as a Probe of the Energetics and Mechanisms of Organometallic Reactions Involving the Formation of Metallacyclobutanes in the Gas Phase

Product kinetic energy release distributions and collision-induced dissociation studies are used to probe the energetics and mechanisms of several gas-phase organometallic reactions involving the formation of metallacyclobutanes.Reaction of atomic cobalt ions with 1-pentene yields Co(C2H4)+.Loss of C3H6 in this process exhibits a bimodal kinetic energy release distribution.The low-energy portion can be modeled using statistical phase space theory by assuming that propylene is eliminated.The high-energy portion of the distribution is similar to that observed for the decarbonylation of cyclobutanone by Co+ to yield Co(CO)+.It is inferred for both systems that cyclopropane elimination is being observed with a tight transition state and a reverse activation energy.The characteristically broad kinetic energy release distributions cannot be described by statistical theories.Similar results are observed with Fe+ as a reactant.In this case, however, the reaction with 1-pentene leads to a broadened rather than a bimodal distribution.These arguments are substantiated using product distributions measured in collision-induced dissociation studies of various adducts which might have structures analogous to those invoked for the reactions of Co+ and Fe+ with cyclobutanone.Metastable loss of CO is also observed in these reactions.Fitting the statistical phase space theory to the measured distribution yields a heat of formation for the cobaltacyclobutane ion of 274+/- 5kcal/mol.The heat of formation (0 K) of the ferracyclobutane ion is less well determined but is approximately 268 kcal/mol.These are substantially higher (by 27 and 16 kcal/mol, respectively) than those for the corresponding isomeric propylene complexes.From these measurements, we estimate strain energies of cobaltacyclobutane and ferracyclobutane to be 22 and 18 kcal/mol, respectively, to be compared with 26 kcal/mol for cyclobutane.