Preparation of photodegradable oligomers containing metal-metal bonds using ADMET

Ginger V. Shultz; Orion B. Berryman; Lev N. Zakharov; David R. Tyler

doi:10.1007/s10904-007-9174-8

Preparation of photodegradable oligomers containing metal-metal bonds using ADMET

Ginger V. Shultz, Orion B. Berryman, Lev N. Zakharov, David R. Tyler

Chemistry

University of Oregon

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

17 Scopus citations

Abstract

ADMET was evaluated as a method for preparing organometallic polymers with metal-metal bonds in the main chain. The Cp ₂Mo ₂CO ₄(Ph ₂P(CH ₂) ₆CH=CH ₂) ₂ complex was synthesized, and the X-ray crystal structure is reported. The molecule did not undergo ADMET polymerization with Grubbs' or Schrock's catalysts. In a control experiment to test if the Ph ₂P(CH ₂) ₆CH=CH ₂ ligand was interfering with the ADMET reaction, the phosphine was reacted with Grubbs' 2nd generation catalyst. The dimerized metathesis product Ph ₂P(CH ₂) ₆CH=CH(CH ₂) ₆PPh ₂ was obtained with no observed degradation or deactivation of the catalyst. To test the inherent ADMET reactivity of the Ph ₂P(CH ₂) ₆CH=CH ₂ ligand when it is bonded to a metal center, the mononuclear cis-Mo(CO) ₄(Ph ₂P(CH ₂) ₆CH=CH ₂) ₂ complex was synthesized and polymerized using Grubbs' 2nd generation catalyst. These control experiments suggest that the inability of Cp ₂Mo ₂CO ₄(Ph ₂P(CH ₂) ₆CH=CH ₂) ₂ to polymerize is not due to electronic effects pertaining to the C=C unit of the Ph ₂P(CH ₂) ₆CH=CH ₂ ligand. Accordingly, steric effects are implicated in the inability of the Cp ₂Mo ₂CO ₄(Ph ₂P(CH ₂) ₆CH=CH ₂) ₂ to polymerize by ADMET.

Original language	English
Pages (from-to)	149-154
Number of pages	6
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	18
Issue number	1
DOIs	https://doi.org/10.1007/s10904-007-9174-8
State	Published - Mar 2008

Keywords

ADMET
Metal-metal bond
Photochemically Degradable polymer

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10.1007/s10904-007-9174-8

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@article{8bda91f4fd45465183624028f9137be6,

title = "Preparation of photodegradable oligomers containing metal-metal bonds using ADMET",

abstract = "ADMET was evaluated as a method for preparing organometallic polymers with metal-metal bonds in the main chain. The Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized, and the X-ray crystal structure is reported. The molecule did not undergo ADMET polymerization with Grubbs' or Schrock's catalysts. In a control experiment to test if the Ph 2P(CH 2) 6CH=CH 2 ligand was interfering with the ADMET reaction, the phosphine was reacted with Grubbs' 2nd generation catalyst. The dimerized metathesis product Ph 2P(CH 2) 6CH=CH(CH 2) 6PPh 2 was obtained with no observed degradation or deactivation of the catalyst. To test the inherent ADMET reactivity of the Ph 2P(CH 2) 6CH=CH 2 ligand when it is bonded to a metal center, the mononuclear cis-Mo(CO) 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized and polymerized using Grubbs' 2nd generation catalyst. These control experiments suggest that the inability of Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize is not due to electronic effects pertaining to the C=C unit of the Ph 2P(CH 2) 6CH=CH 2 ligand. Accordingly, steric effects are implicated in the inability of the Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize by ADMET.",

keywords = "ADMET, Metal-metal bond, Photochemically Degradable polymer",

author = "Shultz, {Ginger V.} and Berryman, {Orion B.} and Zakharov, {Lev N.} and Tyler, {David R.}",

note = "Funding Information: Acknowledgments Acknowledgment is made to the Petroleum Research Fund, administered by the American Chemical Society and to the National Science Foundation (DGE-0231997).",

year = "2008",

month = mar,

doi = "10.1007/s10904-007-9174-8",

language = "English",

volume = "18",

pages = "149--154",

journal = "Journal of Inorganic and Organometallic Polymers and Materials",

issn = "1574-1443",

publisher = "Springer New York",

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T1 - Preparation of photodegradable oligomers containing metal-metal bonds using ADMET

AU - Shultz, Ginger V.

AU - Berryman, Orion B.

AU - Zakharov, Lev N.

AU - Tyler, David R.

N1 - Funding Information: Acknowledgments Acknowledgment is made to the Petroleum Research Fund, administered by the American Chemical Society and to the National Science Foundation (DGE-0231997).

PY - 2008/3

Y1 - 2008/3

N2 - ADMET was evaluated as a method for preparing organometallic polymers with metal-metal bonds in the main chain. The Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized, and the X-ray crystal structure is reported. The molecule did not undergo ADMET polymerization with Grubbs' or Schrock's catalysts. In a control experiment to test if the Ph 2P(CH 2) 6CH=CH 2 ligand was interfering with the ADMET reaction, the phosphine was reacted with Grubbs' 2nd generation catalyst. The dimerized metathesis product Ph 2P(CH 2) 6CH=CH(CH 2) 6PPh 2 was obtained with no observed degradation or deactivation of the catalyst. To test the inherent ADMET reactivity of the Ph 2P(CH 2) 6CH=CH 2 ligand when it is bonded to a metal center, the mononuclear cis-Mo(CO) 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized and polymerized using Grubbs' 2nd generation catalyst. These control experiments suggest that the inability of Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize is not due to electronic effects pertaining to the C=C unit of the Ph 2P(CH 2) 6CH=CH 2 ligand. Accordingly, steric effects are implicated in the inability of the Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize by ADMET.

AB - ADMET was evaluated as a method for preparing organometallic polymers with metal-metal bonds in the main chain. The Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized, and the X-ray crystal structure is reported. The molecule did not undergo ADMET polymerization with Grubbs' or Schrock's catalysts. In a control experiment to test if the Ph 2P(CH 2) 6CH=CH 2 ligand was interfering with the ADMET reaction, the phosphine was reacted with Grubbs' 2nd generation catalyst. The dimerized metathesis product Ph 2P(CH 2) 6CH=CH(CH 2) 6PPh 2 was obtained with no observed degradation or deactivation of the catalyst. To test the inherent ADMET reactivity of the Ph 2P(CH 2) 6CH=CH 2 ligand when it is bonded to a metal center, the mononuclear cis-Mo(CO) 4(Ph 2P(CH 2) 6CH=CH 2) 2 complex was synthesized and polymerized using Grubbs' 2nd generation catalyst. These control experiments suggest that the inability of Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize is not due to electronic effects pertaining to the C=C unit of the Ph 2P(CH 2) 6CH=CH 2 ligand. Accordingly, steric effects are implicated in the inability of the Cp 2Mo 2CO 4(Ph 2P(CH 2) 6CH=CH 2) 2 to polymerize by ADMET.

KW - ADMET

KW - Metal-metal bond

KW - Photochemically Degradable polymer

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M3 - Article

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SN - 1574-1443

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SP - 149

EP - 154

JO - Journal of Inorganic and Organometallic Polymers and Materials

JF - Journal of Inorganic and Organometallic Polymers and Materials

IS - 1

ER -

Preparation of photodegradable oligomers containing metal-metal bonds using ADMET

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