Neutral N-O chelated palladium(II) complexes: Syntheses, characterization, and reactivity

Myeongsoon Kang; Ayusman Sen

doi:10.1021/om050126a

Neutral N-O chelated palladium(II) complexes: Syntheses, characterization, and reactivity

Myeongsoon Kang, Ayusman Sen

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32 Citations (SciVal)

Abstract

A series of neutral salicylaldiminato Pd(II) complexes, Pd(Me)(Ph-CH=N-R′)[3- ^tBu-2-(O)-C ₆H ₃-CH=N-2,6-di ⁱPr-C ₆H ₃] (R = CH ₃, n-Pr, tert-Bu, Ph, benzyl) (3a-3e) and Pd(Me)[2-(CH=N-t-Bu)-Py][3- ^tBu-2-(O)C ₆H ₃-CH=N-2,6-di- ⁱPr-C ₆H ₃] (4), have been synthesized and characterized. The structures of complexes 3a, 3c-3e, and 4 have been confirmed by X-ray analysis. NMR studies utilizing 3c indicate that the insertion of CO into the Pd-Me bond occurs through a five-coordinate intermediate. The acyl compounds in turn undergo imine insertion. The neutral complexes 3a-3e show moderate catalytic activity for the polymerization of methyl acrylate at ambient temperature. However, a radical rather than vinyl insertion mechanism appears to be operative.

Original language	English (US)
Pages (from-to)	3508-3515
Number of pages	8
Journal	Organometallics
Volume	24
Issue number	14
DOIs	https://doi.org/10.1021/om050126a
State	Published - Jul 4 2005

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{0d7e35aacead4d51a6b7f2d84f92a293,

title = "Neutral N-O chelated palladium(II) complexes: Syntheses, characterization, and reactivity",

abstract = "A series of neutral salicylaldiminato Pd(II) complexes, Pd(Me)(Ph-CH=N-R′)[3- tBu-2-(O)-C 6H 3-CH=N-2,6-di iPr-C 6H 3] (R = CH 3, n-Pr, tert-Bu, Ph, benzyl) (3a-3e) and Pd(Me)[2-(CH=N-t-Bu)-Py][3- tBu-2-(O)C 6H 3-CH=N-2,6-di- iPr-C 6H 3] (4), have been synthesized and characterized. The structures of complexes 3a, 3c-3e, and 4 have been confirmed by X-ray analysis. NMR studies utilizing 3c indicate that the insertion of CO into the Pd-Me bond occurs through a five-coordinate intermediate. The acyl compounds in turn undergo imine insertion. The neutral complexes 3a-3e show moderate catalytic activity for the polymerization of methyl acrylate at ambient temperature. However, a radical rather than vinyl insertion mechanism appears to be operative.",

author = "Myeongsoon Kang and Ayusman Sen",

year = "2005",

month = jul,

day = "4",

doi = "10.1021/om050126a",

language = "English (US)",

volume = "24",

pages = "3508--3515",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Neutral N-O chelated palladium(II) complexes

T2 - Syntheses, characterization, and reactivity

AU - Kang, Myeongsoon

AU - Sen, Ayusman

PY - 2005/7/4

Y1 - 2005/7/4

N2 - A series of neutral salicylaldiminato Pd(II) complexes, Pd(Me)(Ph-CH=N-R′)[3- tBu-2-(O)-C 6H 3-CH=N-2,6-di iPr-C 6H 3] (R = CH 3, n-Pr, tert-Bu, Ph, benzyl) (3a-3e) and Pd(Me)[2-(CH=N-t-Bu)-Py][3- tBu-2-(O)C 6H 3-CH=N-2,6-di- iPr-C 6H 3] (4), have been synthesized and characterized. The structures of complexes 3a, 3c-3e, and 4 have been confirmed by X-ray analysis. NMR studies utilizing 3c indicate that the insertion of CO into the Pd-Me bond occurs through a five-coordinate intermediate. The acyl compounds in turn undergo imine insertion. The neutral complexes 3a-3e show moderate catalytic activity for the polymerization of methyl acrylate at ambient temperature. However, a radical rather than vinyl insertion mechanism appears to be operative.

AB - A series of neutral salicylaldiminato Pd(II) complexes, Pd(Me)(Ph-CH=N-R′)[3- tBu-2-(O)-C 6H 3-CH=N-2,6-di iPr-C 6H 3] (R = CH 3, n-Pr, tert-Bu, Ph, benzyl) (3a-3e) and Pd(Me)[2-(CH=N-t-Bu)-Py][3- tBu-2-(O)C 6H 3-CH=N-2,6-di- iPr-C 6H 3] (4), have been synthesized and characterized. The structures of complexes 3a, 3c-3e, and 4 have been confirmed by X-ray analysis. NMR studies utilizing 3c indicate that the insertion of CO into the Pd-Me bond occurs through a five-coordinate intermediate. The acyl compounds in turn undergo imine insertion. The neutral complexes 3a-3e show moderate catalytic activity for the polymerization of methyl acrylate at ambient temperature. However, a radical rather than vinyl insertion mechanism appears to be operative.

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DO - 10.1021/om050126a

M3 - Article

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JO - Organometallics

JF - Organometallics

IS - 14

ER -

Neutral N-O chelated palladium(II) complexes: Syntheses, characterization, and reactivity

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