Side chain functionalized η5-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

Thomas Reiner; Dominik Jantke; Andreas Raba; Alexander N. Marziale; Jörg Eppinger

doi:10.1016/j.jorganchem.2009.01.056

Side chain functionalized η⁵-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

Thomas Reiner, Dominik Jantke, Andreas Raba, Alexander N. Marziale, Jörg Eppinger^*

^*Corresponding author for this work

Research output: Contribution to journal › Short survey › peer-review

21 Scopus citations

Abstract

Conversion of 2-(2,3,4,5-tetramethylcyclopentadien)ethylamine tautomere C₅Me₄H₂(CHCH₂)NH₂ (1) with MCl₃ · n H₂O (M = Rh, Ir) under acidic conditions gives the respective μ-chloro-bridged chelates [(η⁵-Me₄Cp(CH₂)₂NH₃)RhCl₂]₂Cl₂ (2) and [(η⁵-Me₄Cp(CH₂)₂NH₃)IrCl₂]₂Cl₂ (3). The dimeric complexes are received as ammonium salts and thus display good solubility in strong donor solvents such as water and DMSO. Addition of triphenyl phosphine converts Rh-dimer 2 into the mononuclear phosphine complex 4. Under basic conditions, no intramolecular coordination of the pendant NH₂ is observed and thus the primary amino group of 4 reacts selectively with succinic anhydride by formation of a peptide bond. Hence, the electrophilic metal center and the latent nucleophilic nitrogen, which represent complementary functionalities, can be addressed separately under the appropriate reaction conditions.

Original language	English (US)
Pages (from-to)	1934-1937
Number of pages	4
Journal	Journal of Organometallic Chemistry
Volume	694
Issue number	12
DOIs	https://doi.org/10.1016/j.jorganchem.2009.01.056
State	Published - May 15 2009
Externally published	Yes

Bibliographical note

Funding Information:
We thank the Stifterverband für die Deutsche Wissenschaft (project 11047), the Elitenetzwerk Bayern e.V. (graduate fellowships for T.R. and A.N.M.) and the IDK NanoCat for generous financial support.

Keywords

Cyclopentadiene derivative
Functionalized metal complexes
Iridium
Metal peptide conjugation
Rhodium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jorganchem.2009.01.056

Cite this

@article{8b295d29a93441df82ffcc9d3435fbd7,

title = "Side chain functionalized η5-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group",

abstract = "Conversion of 2-(2,3,4,5-tetramethylcyclopentadien)ethylamine tautomere C5Me4H2(CHCH2)NH2 (1) with MCl3 · n H2O (M = Rh, Ir) under acidic conditions gives the respective μ-chloro-bridged chelates [(η5-Me4Cp(CH2)2NH3)RhCl2]2Cl2 (2) and [(η5-Me4Cp(CH2)2NH3)IrCl2]2Cl2 (3). The dimeric complexes are received as ammonium salts and thus display good solubility in strong donor solvents such as water and DMSO. Addition of triphenyl phosphine converts Rh-dimer 2 into the mononuclear phosphine complex 4. Under basic conditions, no intramolecular coordination of the pendant NH2 is observed and thus the primary amino group of 4 reacts selectively with succinic anhydride by formation of a peptide bond. Hence, the electrophilic metal center and the latent nucleophilic nitrogen, which represent complementary functionalities, can be addressed separately under the appropriate reaction conditions.",

keywords = "Cyclopentadiene derivative, Functionalized metal complexes, Iridium, Metal peptide conjugation, Rhodium",

author = "Thomas Reiner and Dominik Jantke and Andreas Raba and Marziale, {Alexander N.} and J{\"o}rg Eppinger",

note = "Funding Information: We thank the Stifterverband f{\"u}r die Deutsche Wissenschaft (project 11047), the Elitenetzwerk Bayern e.V. (graduate fellowships for T.R. and A.N.M.) and the IDK NanoCat for generous financial support.",

year = "2009",

month = may,

day = "15",

doi = "10.1016/j.jorganchem.2009.01.056",

language = "English (US)",

volume = "694",

pages = "1934--1937",

journal = "Journal of Organometallic Chemistry",

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publisher = "Elsevier",

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TY - JOUR

T1 - Side chain functionalized η5-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

AU - Reiner, Thomas

AU - Jantke, Dominik

AU - Raba, Andreas

AU - Marziale, Alexander N.

AU - Eppinger, Jörg

N1 - Funding Information: We thank the Stifterverband für die Deutsche Wissenschaft (project 11047), the Elitenetzwerk Bayern e.V. (graduate fellowships for T.R. and A.N.M.) and the IDK NanoCat for generous financial support.

PY - 2009/5/15

Y1 - 2009/5/15

N2 - Conversion of 2-(2,3,4,5-tetramethylcyclopentadien)ethylamine tautomere C5Me4H2(CHCH2)NH2 (1) with MCl3 · n H2O (M = Rh, Ir) under acidic conditions gives the respective μ-chloro-bridged chelates [(η5-Me4Cp(CH2)2NH3)RhCl2]2Cl2 (2) and [(η5-Me4Cp(CH2)2NH3)IrCl2]2Cl2 (3). The dimeric complexes are received as ammonium salts and thus display good solubility in strong donor solvents such as water and DMSO. Addition of triphenyl phosphine converts Rh-dimer 2 into the mononuclear phosphine complex 4. Under basic conditions, no intramolecular coordination of the pendant NH2 is observed and thus the primary amino group of 4 reacts selectively with succinic anhydride by formation of a peptide bond. Hence, the electrophilic metal center and the latent nucleophilic nitrogen, which represent complementary functionalities, can be addressed separately under the appropriate reaction conditions.

AB - Conversion of 2-(2,3,4,5-tetramethylcyclopentadien)ethylamine tautomere C5Me4H2(CHCH2)NH2 (1) with MCl3 · n H2O (M = Rh, Ir) under acidic conditions gives the respective μ-chloro-bridged chelates [(η5-Me4Cp(CH2)2NH3)RhCl2]2Cl2 (2) and [(η5-Me4Cp(CH2)2NH3)IrCl2]2Cl2 (3). The dimeric complexes are received as ammonium salts and thus display good solubility in strong donor solvents such as water and DMSO. Addition of triphenyl phosphine converts Rh-dimer 2 into the mononuclear phosphine complex 4. Under basic conditions, no intramolecular coordination of the pendant NH2 is observed and thus the primary amino group of 4 reacts selectively with succinic anhydride by formation of a peptide bond. Hence, the electrophilic metal center and the latent nucleophilic nitrogen, which represent complementary functionalities, can be addressed separately under the appropriate reaction conditions.

KW - Cyclopentadiene derivative

KW - Functionalized metal complexes

KW - Iridium

KW - Metal peptide conjugation

KW - Rhodium

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