Formation of elastomeric polypropylene promoted by a dynamic octahedral titanium complex

Elena Smolensky; Moshe Kapon; J. Derek Woollins; Moris S. Eisen

doi:10.1021/om050015b

Formation of elastomeric polypropylene promoted by a dynamic octahedral titanium complex

Elena Smolensky, Moshe Kapon, J. Derek Woollins, Moris S. Eisen^*

^*Corresponding author for this work

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

52 Scopus citations

Abstract

The complex Ti(Ph₂PNpy)(NEt₂)₂ (2) was prepared by the reaction between 2 equiv of the neutral ligand Pt ₂PNHpy (1) and 1 equiv of the homoleptic titanium tetrakis(diethylamine). Complex 2 exhibits two dynamic processes as a function of the temperature. An equilibrium among the diphenylphosphino moieties and a strong agostic interaction between the titanium atom and one of the hydrogens of each of the methylene groups of the diethylamido ligand. The strength of the chelating ligand was studied by its reaction with ethylamine, producing the imido complex 3, showing that during the transformation 2 → 3 the pyridine rings of the ligand are able to dissociate and recoordinate with different stereochemistries. In the polymerization of propylene by complex 2 activated by MAO, elastomeric polymers are obtained. The elastomeric polymers are a result of monomer insertions into two enantiomerically close configuration complexes, as is encountered in cationic nonbridged metallocenes.

Original language	English
Pages (from-to)	3255-3265
Number of pages	11
Journal	Organometallics
Volume	24
Issue number	13
DOIs	https://doi.org/10.1021/om050015b
State	Published - 20 Jun 2005
Externally published	Yes

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title = "Formation of elastomeric polypropylene promoted by a dynamic octahedral titanium complex",

abstract = "The complex Ti(Ph2PNpy)(NEt2)2 (2) was prepared by the reaction between 2 equiv of the neutral ligand Pt 2PNHpy (1) and 1 equiv of the homoleptic titanium tetrakis(diethylamine). Complex 2 exhibits two dynamic processes as a function of the temperature. An equilibrium among the diphenylphosphino moieties and a strong agostic interaction between the titanium atom and one of the hydrogens of each of the methylene groups of the diethylamido ligand. The strength of the chelating ligand was studied by its reaction with ethylamine, producing the imido complex 3, showing that during the transformation 2 → 3 the pyridine rings of the ligand are able to dissociate and recoordinate with different stereochemistries. In the polymerization of propylene by complex 2 activated by MAO, elastomeric polymers are obtained. The elastomeric polymers are a result of monomer insertions into two enantiomerically close configuration complexes, as is encountered in cationic nonbridged metallocenes.",

author = "Elena Smolensky and Moshe Kapon and Woollins, {J. Derek} and Eisen, {Moris S.}",

year = "2005",

month = jun,

day = "20",

doi = "10.1021/om050015b",

language = "英语",

volume = "24",

pages = "3255--3265",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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}

TY - JOUR

T1 - Formation of elastomeric polypropylene promoted by a dynamic octahedral titanium complex

AU - Smolensky, Elena

AU - Kapon, Moshe

AU - Woollins, J. Derek

AU - Eisen, Moris S.

PY - 2005/6/20

Y1 - 2005/6/20

N2 - The complex Ti(Ph2PNpy)(NEt2)2 (2) was prepared by the reaction between 2 equiv of the neutral ligand Pt 2PNHpy (1) and 1 equiv of the homoleptic titanium tetrakis(diethylamine). Complex 2 exhibits two dynamic processes as a function of the temperature. An equilibrium among the diphenylphosphino moieties and a strong agostic interaction between the titanium atom and one of the hydrogens of each of the methylene groups of the diethylamido ligand. The strength of the chelating ligand was studied by its reaction with ethylamine, producing the imido complex 3, showing that during the transformation 2 → 3 the pyridine rings of the ligand are able to dissociate and recoordinate with different stereochemistries. In the polymerization of propylene by complex 2 activated by MAO, elastomeric polymers are obtained. The elastomeric polymers are a result of monomer insertions into two enantiomerically close configuration complexes, as is encountered in cationic nonbridged metallocenes.

AB - The complex Ti(Ph2PNpy)(NEt2)2 (2) was prepared by the reaction between 2 equiv of the neutral ligand Pt 2PNHpy (1) and 1 equiv of the homoleptic titanium tetrakis(diethylamine). Complex 2 exhibits two dynamic processes as a function of the temperature. An equilibrium among the diphenylphosphino moieties and a strong agostic interaction between the titanium atom and one of the hydrogens of each of the methylene groups of the diethylamido ligand. The strength of the chelating ligand was studied by its reaction with ethylamine, producing the imido complex 3, showing that during the transformation 2 → 3 the pyridine rings of the ligand are able to dissociate and recoordinate with different stereochemistries. In the polymerization of propylene by complex 2 activated by MAO, elastomeric polymers are obtained. The elastomeric polymers are a result of monomer insertions into two enantiomerically close configuration complexes, as is encountered in cationic nonbridged metallocenes.

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U2 - 10.1021/om050015b

DO - 10.1021/om050015b

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AN - SCOPUS:23144448291

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VL - 24

SP - 3255

EP - 3265

JO - Organometallics

JF - Organometallics

IS - 13

ER -

Formation of elastomeric polypropylene promoted by a dynamic octahedral titanium complex

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