Synthesis, structure, and reactivity of new rhodium and iridium complexes, bearing a highly electron-donating PNP system. Iridium-mediated vinylic C-H bond activation

Dominik Hermann, Mark Gandelman, Haim Rozenberg, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

111 Citations (Scopus)

Abstract

Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphi-nomethl)pyridine] (1) with [Rh(COE)2Cl]2 (COE = cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH3CN)]BF4 (3) and [Rh(PNP)(C2H4)]SO3CF3 (4) were obtained in reaction of 1 with [(COE)2Rh(CH3CN)2]BF4 and [(C2H4)2Rh(THF)2]SO3CF 3, respectively. Upon reaction of the PNP ligand 1 with [Ir(COE)2Cl]2, facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C8H13)] (5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD)2]BF4 (COD = cyclooctadiene) in RCN (R = CH3, CH(CH3)2, C(CH3)3) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C8H11)]BF4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H)2]BF4 (R = CH3, C(CH3)3) (7a,b).

Original languageEnglish
Pages (from-to)812-818
Number of pages7
JournalOrganometallics
Volume21
Issue number5
DOIs
Publication statusPublished - Mar 4 2002

Fingerprint

Bearings (structural)
Iridium
Rhodium
iridium
rhodium
crack opening displacement
reactivity
Chemical activation
activation
Ligands
ligands
Electrons
synthesis
dihydrides
electrons
room temperature
insertion
pyridines
methylidyne
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis, structure, and reactivity of new rhodium and iridium complexes, bearing a highly electron-donating PNP system. Iridium-mediated vinylic C-H bond activation. / Hermann, Dominik; Gandelman, Mark; Rozenberg, Haim; Shimon, Linda J W; Milstein, David.

In: Organometallics, Vol. 21, No. 5, 04.03.2002, p. 812-818.

Research output: Contribution to journalArticle

@article{20307f0202334fd694d7a8f753b238c4,
title = "Synthesis, structure, and reactivity of new rhodium and iridium complexes, bearing a highly electron-donating PNP system. Iridium-mediated vinylic C-H bond activation",
abstract = "Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphi-nomethl)pyridine] (1) with [Rh(COE)2Cl]2 (COE = cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH3CN)]BF4 (3) and [Rh(PNP)(C2H4)]SO3CF3 (4) were obtained in reaction of 1 with [(COE)2Rh(CH3CN)2]BF4 and [(C2H4)2Rh(THF)2]SO3CF 3, respectively. Upon reaction of the PNP ligand 1 with [Ir(COE)2Cl]2, facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C8H13)] (5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD)2]BF4 (COD = cyclooctadiene) in RCN (R = CH3, CH(CH3)2, C(CH3)3) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C8H11)]BF4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H)2]BF4 (R = CH3, C(CH3)3) (7a,b).",
author = "Dominik Hermann and Mark Gandelman and Haim Rozenberg and Shimon, {Linda J W} and David Milstein",
year = "2002",
month = "3",
day = "4",
doi = "10.1021/om010719v",
language = "English",
volume = "21",
pages = "812--818",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Synthesis, structure, and reactivity of new rhodium and iridium complexes, bearing a highly electron-donating PNP system. Iridium-mediated vinylic C-H bond activation

AU - Hermann, Dominik

AU - Gandelman, Mark

AU - Rozenberg, Haim

AU - Shimon, Linda J W

AU - Milstein, David

PY - 2002/3/4

Y1 - 2002/3/4

N2 - Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphi-nomethl)pyridine] (1) with [Rh(COE)2Cl]2 (COE = cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH3CN)]BF4 (3) and [Rh(PNP)(C2H4)]SO3CF3 (4) were obtained in reaction of 1 with [(COE)2Rh(CH3CN)2]BF4 and [(C2H4)2Rh(THF)2]SO3CF 3, respectively. Upon reaction of the PNP ligand 1 with [Ir(COE)2Cl]2, facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C8H13)] (5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD)2]BF4 (COD = cyclooctadiene) in RCN (R = CH3, CH(CH3)2, C(CH3)3) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C8H11)]BF4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H)2]BF4 (R = CH3, C(CH3)3) (7a,b).

AB - Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphi-nomethl)pyridine] (1) with [Rh(COE)2Cl]2 (COE = cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH3CN)]BF4 (3) and [Rh(PNP)(C2H4)]SO3CF3 (4) were obtained in reaction of 1 with [(COE)2Rh(CH3CN)2]BF4 and [(C2H4)2Rh(THF)2]SO3CF 3, respectively. Upon reaction of the PNP ligand 1 with [Ir(COE)2Cl]2, facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C8H13)] (5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD)2]BF4 (COD = cyclooctadiene) in RCN (R = CH3, CH(CH3)2, C(CH3)3) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C8H11)]BF4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H)2]BF4 (R = CH3, C(CH3)3) (7a,b).

UR - http://www.scopus.com/inward/record.url?scp=0000647080&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000647080&partnerID=8YFLogxK

U2 - 10.1021/om010719v

DO - 10.1021/om010719v

M3 - Article

VL - 21

SP - 812

EP - 818

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 5

ER -