Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts

J K  Huang; H J  Schanz; E D  Stevens; Steven Patrick Nolan

doi:10.1021/om990788y

Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts

J K Huang, H J Schanz, E D Stevens, Steven Patrick Nolan

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251 Citations (Scopus)

Abstract

The exchange reaction of one phosphine ligand in Cl-2(PCy3)(2)Ru=CHPh (1; Cy = cyclohexyl, C6H11 with the sterically demanding carbene ligands 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), 1,3-bis(4-methylphenyl)imidazol-2-yliden (ITol), and 1,3-bis(4-chlorophenyl)imidazol-2-ylidene (IpCl) leads to the isolation of the new complexes (PCy3)(IMes)Cl2Ru=CHPh (2), (PCy3)(ITol)Cl2Ru=CHPh (3), and (PCy3)(IpCl)Cl2Ru=CHPh (4). Similarly, one IMes ligand can be substituted for one PCyp(3) ligand in Cl-2(PCyp(3))(2)Ru=CHCH=C(CH3)(2) (5; Cyp = cyclopentyl, C5H9) to produce (PCyp(3))(IMes)Cl2Ru=CHPh (6) in high yield. X-ray structure analysis of 6 confirmed a near-square-pyramidal coordination sphere around the metal center. Improved catalytic properties and thermal stability are observed for 2 and 6 in comparison to the parent 1 and 5.

Original language	English
Pages (from-to)	5375-5380
Number of pages	6
Journal	Organometallics
Volume	18
Issue number	25
DOIs	https://doi.org/10.1021/om990788y
Publication status	Published - 6 Dec 1999

Keywords

N-HETEROCYCLIC CARBENES
STRAIN CYCLIC OLEFINS
POLYMERIZATION
COMPLEXES
RUCL2(=CHR')(PR(3))(2)
NORBORNENE
WATER
ROMP

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@article{32c8d8cce0b4472a83a863031c41cfb3,

title = "Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts",

abstract = "The exchange reaction of one phosphine ligand in Cl-2(PCy3)(2)Ru=CHPh (1; Cy = cyclohexyl, C6H11 with the sterically demanding carbene ligands 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), 1,3-bis(4-methylphenyl)imidazol-2-yliden (ITol), and 1,3-bis(4-chlorophenyl)imidazol-2-ylidene (IpCl) leads to the isolation of the new complexes (PCy3)(IMes)Cl2Ru=CHPh (2), (PCy3)(ITol)Cl2Ru=CHPh (3), and (PCy3)(IpCl)Cl2Ru=CHPh (4). Similarly, one IMes ligand can be substituted for one PCyp(3) ligand in Cl-2(PCyp(3))(2)Ru=CHCH=C(CH3)(2) (5; Cyp = cyclopentyl, C5H9) to produce (PCyp(3))(IMes)Cl2Ru=CHPh (6) in high yield. X-ray structure analysis of 6 confirmed a near-square-pyramidal coordination sphere around the metal center. Improved catalytic properties and thermal stability are observed for 2 and 6 in comparison to the parent 1 and 5.",

keywords = "N-HETEROCYCLIC CARBENES, STRAIN CYCLIC OLEFINS, POLYMERIZATION, COMPLEXES, RUCL2(=CHR')(PR(3))(2), NORBORNENE, WATER, ROMP",

author = "Huang, {J K} and Schanz, {H J} and Stevens, {E D} and Nolan, {Steven Patrick}",

year = "1999",

month = dec,

day = "6",

doi = "10.1021/om990788y",

language = "English",

volume = "18",

pages = "5375--5380",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

number = "25",

}

TY - JOUR

T1 - Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts

AU - Huang, J K

AU - Schanz, H J

AU - Stevens, E D

AU - Nolan, Steven Patrick

PY - 1999/12/6

Y1 - 1999/12/6

N2 - The exchange reaction of one phosphine ligand in Cl-2(PCy3)(2)Ru=CHPh (1; Cy = cyclohexyl, C6H11 with the sterically demanding carbene ligands 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), 1,3-bis(4-methylphenyl)imidazol-2-yliden (ITol), and 1,3-bis(4-chlorophenyl)imidazol-2-ylidene (IpCl) leads to the isolation of the new complexes (PCy3)(IMes)Cl2Ru=CHPh (2), (PCy3)(ITol)Cl2Ru=CHPh (3), and (PCy3)(IpCl)Cl2Ru=CHPh (4). Similarly, one IMes ligand can be substituted for one PCyp(3) ligand in Cl-2(PCyp(3))(2)Ru=CHCH=C(CH3)(2) (5; Cyp = cyclopentyl, C5H9) to produce (PCyp(3))(IMes)Cl2Ru=CHPh (6) in high yield. X-ray structure analysis of 6 confirmed a near-square-pyramidal coordination sphere around the metal center. Improved catalytic properties and thermal stability are observed for 2 and 6 in comparison to the parent 1 and 5.

AB - The exchange reaction of one phosphine ligand in Cl-2(PCy3)(2)Ru=CHPh (1; Cy = cyclohexyl, C6H11 with the sterically demanding carbene ligands 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), 1,3-bis(4-methylphenyl)imidazol-2-yliden (ITol), and 1,3-bis(4-chlorophenyl)imidazol-2-ylidene (IpCl) leads to the isolation of the new complexes (PCy3)(IMes)Cl2Ru=CHPh (2), (PCy3)(ITol)Cl2Ru=CHPh (3), and (PCy3)(IpCl)Cl2Ru=CHPh (4). Similarly, one IMes ligand can be substituted for one PCyp(3) ligand in Cl-2(PCyp(3))(2)Ru=CHCH=C(CH3)(2) (5; Cyp = cyclopentyl, C5H9) to produce (PCyp(3))(IMes)Cl2Ru=CHPh (6) in high yield. X-ray structure analysis of 6 confirmed a near-square-pyramidal coordination sphere around the metal center. Improved catalytic properties and thermal stability are observed for 2 and 6 in comparison to the parent 1 and 5.

KW - N-HETEROCYCLIC CARBENES

KW - STRAIN CYCLIC OLEFINS

KW - POLYMERIZATION

KW - COMPLEXES

KW - RUCL2(=CHR')(PR(3))(2)

KW - NORBORNENE

KW - WATER

KW - ROMP

U2 - 10.1021/om990788y

DO - 10.1021/om990788y

M3 - Article

SN - 0276-7333

VL - 18

SP - 5375

EP - 5380

JO - Organometallics

JF - Organometallics

IS - 25

ER -

Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts

Abstract

Keywords

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