Mechanism of endo-exo interconversion in η3-allyl Cp complexes: A longstanding unresolved issue

Alireza Ariafard; Siwei Bi; Zhenyang Lin

doi:10.1021/om050161h

Mechanism of endo-exo interconversion in η3-allyl Cp complexes: A longstanding unresolved issue

Alireza Ariafard, Siwei Bi, Zhenyang Lin^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

48 Citations (Scopus)

Abstract

Density functional theory studies of the d⁶ allyl complexes CpM(CO)(η³-C₃H₅) (M = Fe, Ru) and the d⁴ allyl complex CpMo(CO)₂(η³-C ₃H₅) show that the interconversion for CpMo(CO) ₂(η³-C₃H₅) through the η³ → η³ →η³ pathway is intrinsically more favorable than the η³ → η¹→η³ pathway. However, the η³ transition states for CpM(CO)(η³-C₃H₅) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.

Original language	English
Pages (from-to)	2241-2244
Number of pages	4
Journal	Organometallics
Volume	24
Issue number	10
DOIs	https://doi.org/10.1021/om050161h
Publication status	Published - 9 May 2005
Externally published	Yes

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title = "Mechanism of endo-exo interconversion in η3-allyl Cp complexes: A longstanding unresolved issue",

abstract = "Density functional theory studies of the d6 allyl complexes CpM(CO)(η3-C3H5) (M = Fe, Ru) and the d4 allyl complex CpMo(CO)2(η3-C 3H5) show that the interconversion for CpMo(CO) 2(η3-C3H5) through the η3 → η3 →η3 pathway is intrinsically more favorable than the η3 → η1→η3 pathway. However, the η3 transition states for CpM(CO)(η3-C3H5) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.",

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year = "2005",

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T1 - Mechanism of endo-exo interconversion in η3-allyl Cp complexes

T2 - A longstanding unresolved issue

AU - Ariafard, Alireza

AU - Bi, Siwei

AU - Lin, Zhenyang

PY - 2005/5/9

Y1 - 2005/5/9

N2 - Density functional theory studies of the d6 allyl complexes CpM(CO)(η3-C3H5) (M = Fe, Ru) and the d4 allyl complex CpMo(CO)2(η3-C 3H5) show that the interconversion for CpMo(CO) 2(η3-C3H5) through the η3 → η3 →η3 pathway is intrinsically more favorable than the η3 → η1→η3 pathway. However, the η3 transition states for CpM(CO)(η3-C3H5) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.

AB - Density functional theory studies of the d6 allyl complexes CpM(CO)(η3-C3H5) (M = Fe, Ru) and the d4 allyl complex CpMo(CO)2(η3-C 3H5) show that the interconversion for CpMo(CO) 2(η3-C3H5) through the η3 → η3 →η3 pathway is intrinsically more favorable than the η3 → η1→η3 pathway. However, the η3 transition states for CpM(CO)(η3-C3H5) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.

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U2 - 10.1021/om050161h

DO - 10.1021/om050161h

M3 - Article

AN - SCOPUS:18844455774

SN - 0276-7333

VL - 24

SP - 2241

EP - 2244

JO - Organometallics

JF - Organometallics

IS - 10

ER -

Mechanism of endo-exo interconversion in η3-allyl Cp complexes: A longstanding unresolved issue

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