Preparation, structure, and ether cleavage of a mixed hapticity allyl compound of calcium

Phillip Jochmann; Thomas P. Spaniol; Stephen C. Chmely; Timothy P. Hanusa; Jun Okuda

doi:10.1021/om200749f

Preparation, structure, and ether cleavage of a mixed hapticity allyl compound of calcium

Phillip Jochmann, Thomas P. Spaniol, Stephen C. Chmely, Timothy P. Hanusa, Jun Okuda

Agricultural & Biological Engineering

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Abstract

The synthesis, characterization, and decomposition pathway of the 18-crown-6 adduct of bis(allyl)calcium [Ca(η¹-C₃H ₅)(η³-C₃H₅)(18-crown-6)] (2) are reported. The solid-state structure of adduct 2 features one σ- and one π-bonded allyl ligand at the metal center. 2 is the first structurally characterized example of a mononuclear calcium complex bearing a purely σ-bound allyl ligand. DFT calculations indicate that [Ca(η ¹-C₃H₅)(η³-C₃H ₅)(18-crown-6)] and [Ca(η¹-C₃H ₅)₂(18-crown-6)] conformations are close in energy. In THF solution, η³-allyl ligands are observed exclusively at both ambient temperature and -95 °C. 2 undergoes rapid cleavage of the crown ether to give vinyl-terminated alcoholates of different chain length with a half-life of t_1/2 = 2.5 h.

Original language	English (US)
Pages (from-to)	5291-5296
Number of pages	6
Journal	Organometallics
Volume	30
Issue number	19
DOIs	https://doi.org/10.1021/om200749f
State	Published - Oct 10 2011

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om200749f

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@article{90794e69841f4863980473c86ac33807,

title = "Preparation, structure, and ether cleavage of a mixed hapticity allyl compound of calcium",

abstract = "The synthesis, characterization, and decomposition pathway of the 18-crown-6 adduct of bis(allyl)calcium [Ca(η1-C3H 5)(η3-C3H5)(18-crown-6)] (2) are reported. The solid-state structure of adduct 2 features one σ- and one π-bonded allyl ligand at the metal center. 2 is the first structurally characterized example of a mononuclear calcium complex bearing a purely σ-bound allyl ligand. DFT calculations indicate that [Ca(η 1-C3H5)(η3-C3H 5)(18-crown-6)] and [Ca(η1-C3H 5)2(18-crown-6)] conformations are close in energy. In THF solution, η3-allyl ligands are observed exclusively at both ambient temperature and -95 °C. 2 undergoes rapid cleavage of the crown ether to give vinyl-terminated alcoholates of different chain length with a half-life of t1/2 = 2.5 h.",

author = "Phillip Jochmann and Spaniol, {Thomas P.} and Chmely, {Stephen C.} and Hanusa, {Timothy P.} and Jun Okuda",

year = "2011",

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doi = "10.1021/om200749f",

language = "English (US)",

volume = "30",

pages = "5291--5296",

journal = "Organometallics",

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TY - JOUR

T1 - Preparation, structure, and ether cleavage of a mixed hapticity allyl compound of calcium

AU - Jochmann, Phillip

AU - Spaniol, Thomas P.

AU - Chmely, Stephen C.

AU - Hanusa, Timothy P.

AU - Okuda, Jun

PY - 2011/10/10

Y1 - 2011/10/10

N2 - The synthesis, characterization, and decomposition pathway of the 18-crown-6 adduct of bis(allyl)calcium [Ca(η1-C3H 5)(η3-C3H5)(18-crown-6)] (2) are reported. The solid-state structure of adduct 2 features one σ- and one π-bonded allyl ligand at the metal center. 2 is the first structurally characterized example of a mononuclear calcium complex bearing a purely σ-bound allyl ligand. DFT calculations indicate that [Ca(η 1-C3H5)(η3-C3H 5)(18-crown-6)] and [Ca(η1-C3H 5)2(18-crown-6)] conformations are close in energy. In THF solution, η3-allyl ligands are observed exclusively at both ambient temperature and -95 °C. 2 undergoes rapid cleavage of the crown ether to give vinyl-terminated alcoholates of different chain length with a half-life of t1/2 = 2.5 h.

AB - The synthesis, characterization, and decomposition pathway of the 18-crown-6 adduct of bis(allyl)calcium [Ca(η1-C3H 5)(η3-C3H5)(18-crown-6)] (2) are reported. The solid-state structure of adduct 2 features one σ- and one π-bonded allyl ligand at the metal center. 2 is the first structurally characterized example of a mononuclear calcium complex bearing a purely σ-bound allyl ligand. DFT calculations indicate that [Ca(η 1-C3H5)(η3-C3H 5)(18-crown-6)] and [Ca(η1-C3H 5)2(18-crown-6)] conformations are close in energy. In THF solution, η3-allyl ligands are observed exclusively at both ambient temperature and -95 °C. 2 undergoes rapid cleavage of the crown ether to give vinyl-terminated alcoholates of different chain length with a half-life of t1/2 = 2.5 h.

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DO - 10.1021/om200749f

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JO - Organometallics

JF - Organometallics

IS - 19

ER -

Preparation, structure, and ether cleavage of a mixed hapticity allyl compound of calcium

Abstract

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