Methacrylate insertion into cationic diimine palladium(II)-alkyl complexes and the synthesis of poly(alkene-mocfc-alkene/carbon monoxide) copolymers

Sachin Borkar; Hemant Yennawar; Ayusman Sen

doi:10.1021/om7006024

Methacrylate insertion into cationic diimine palladium(II)-alkyl complexes and the synthesis of poly(alkene-mocfc-alkene/carbon monoxide) copolymers

Sachin Borkar, Hemant Yennawar, Ayusman Sen

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

32 Scopus citations

Abstract

The reaction of cationic Pd(II) diimine complex [(N∧N)Pd(Me)(L)] [B(Ar_f)₄] ((N∧N) = 2,3-bis(2,6-di- isopropylphenylimino)butane, Ar_f -3,5-(CF₃) ₂C₆H₃, L = Et₂O) with methyl methacrylate results in 1,2-insertion regiochemistry that is opposite ofthat observed with methyl aery late. The enthalpy of activation for MMA insertion is 4 kcal/mol higher than that for the corresponding MA insertion. The MMA-inserted complex can be employed for ethene or 1-hexene homopolymerization and their alternating copolymerization with carbon monoxide. Further, the quasi-living nature of the polymerizations allows the synthesis of poly(hexene-b-hexeneZCO) and poly(ethene-bethene/CO) copolymers.

Original language	English (US)
Pages (from-to)	4711-4714
Number of pages	4
Journal	Organometallics
Volume	26
Issue number	19
DOIs	https://doi.org/10.1021/om7006024
State	Published - Sep 10 2007

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/om7006024

Cite this

@article{8a2255a18e2a411992b759c0ab94e6da,

title = "Methacrylate insertion into cationic diimine palladium(II)-alkyl complexes and the synthesis of poly(alkene-mocfc-alkene/carbon monoxide) copolymers",

abstract = "The reaction of cationic Pd(II) diimine complex [(N∧N)Pd(Me)(L)] [B(Arf)4] ((N∧N) = 2,3-bis(2,6-di- isopropylphenylimino)butane, Arf -3,5-(CF3) 2C6H3, L = Et2O) with methyl methacrylate results in 1,2-insertion regiochemistry that is opposite ofthat observed with methyl aery late. The enthalpy of activation for MMA insertion is 4 kcal/mol higher than that for the corresponding MA insertion. The MMA-inserted complex can be employed for ethene or 1-hexene homopolymerization and their alternating copolymerization with carbon monoxide. Further, the quasi-living nature of the polymerizations allows the synthesis of poly(hexene-b-hexeneZCO) and poly(ethene-bethene/CO) copolymers.",

author = "Sachin Borkar and Hemant Yennawar and Ayusman Sen",

year = "2007",

month = sep,

day = "10",

doi = "10.1021/om7006024",

language = "English (US)",

volume = "26",

pages = "4711--4714",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Methacrylate insertion into cationic diimine palladium(II)-alkyl complexes and the synthesis of poly(alkene-mocfc-alkene/carbon monoxide) copolymers

AU - Borkar, Sachin

AU - Yennawar, Hemant

AU - Sen, Ayusman

PY - 2007/9/10

Y1 - 2007/9/10

N2 - The reaction of cationic Pd(II) diimine complex [(N∧N)Pd(Me)(L)] [B(Arf)4] ((N∧N) = 2,3-bis(2,6-di- isopropylphenylimino)butane, Arf -3,5-(CF3) 2C6H3, L = Et2O) with methyl methacrylate results in 1,2-insertion regiochemistry that is opposite ofthat observed with methyl aery late. The enthalpy of activation for MMA insertion is 4 kcal/mol higher than that for the corresponding MA insertion. The MMA-inserted complex can be employed for ethene or 1-hexene homopolymerization and their alternating copolymerization with carbon monoxide. Further, the quasi-living nature of the polymerizations allows the synthesis of poly(hexene-b-hexeneZCO) and poly(ethene-bethene/CO) copolymers.

AB - The reaction of cationic Pd(II) diimine complex [(N∧N)Pd(Me)(L)] [B(Arf)4] ((N∧N) = 2,3-bis(2,6-di- isopropylphenylimino)butane, Arf -3,5-(CF3) 2C6H3, L = Et2O) with methyl methacrylate results in 1,2-insertion regiochemistry that is opposite ofthat observed with methyl aery late. The enthalpy of activation for MMA insertion is 4 kcal/mol higher than that for the corresponding MA insertion. The MMA-inserted complex can be employed for ethene or 1-hexene homopolymerization and their alternating copolymerization with carbon monoxide. Further, the quasi-living nature of the polymerizations allows the synthesis of poly(hexene-b-hexeneZCO) and poly(ethene-bethene/CO) copolymers.

UR - http://www.scopus.com/inward/record.url?scp=34748880628&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34748880628&partnerID=8YFLogxK

U2 - 10.1021/om7006024

DO - 10.1021/om7006024

M3 - Article

AN - SCOPUS:34748880628

SN - 0276-7333

VL - 26

SP - 4711

EP - 4714

JO - Organometallics

JF - Organometallics

IS - 19

ER -

Methacrylate insertion into cationic diimine palladium(II)-alkyl complexes and the synthesis of poly(alkene-mocfc-alkene/carbon monoxide) copolymers

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this