The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+: An experimental and theoretical examination

Michael Montag; Irena Efremenko; Revital Cohen; Gregory Leitus; Linda J.W. Shimon; Yael Diskin-Posner; Yehoshoa Ben-David; Jan M.L. Martin; David Milstein

doi:10.1002/chem.200801171

The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)₂(phosphine)₂]⁺: An experimental and theoretical examination

Michael Montag, Irena Efremenko, Revital Cohen, Gregory Leitus, Linda J.W. Shimon, Yael Diskin-Posner, Yehoshoa Ben-David, Jan M.L. Martin, David Milstein

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

11 Scopus citations

Abstract

The crystal structure of the new cation ic Rh¹ complex trans-[Rh(CO)₂(L)₂]BF₄ (L = a ²-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar Rh^I complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.

Original language	English
Pages (from-to)	8183-8194
Number of pages	12
Journal	Chemistry - A European Journal
Volume	14
Issue number	27
DOIs	https://doi.org/10.1002/chem.200801171
State	Published - 19 Sep 2008
Externally published	Yes

Keywords

Anagostic interaction
C-H activation
Carbonyl ligands
Phosphines
Rhodium

Access to Document

10.1002/chem.200801171

Cite this

Montag, M., Efremenko, I., Cohen, R., Leitus, G., Shimon, L. J. W., Diskin-Posner, Y., Ben-David, Y., Martin, J. M. L., & Milstein, D. (2008). The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)₂(phosphine)₂]⁺: An experimental and theoretical examination. Chemistry - A European Journal, 14(27), 8183-8194. https://doi.org/10.1002/chem.200801171

@article{aa0aa3b2d7d64708bbef7eca8797a62d,

title = "The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+: An experimental and theoretical examination",

abstract = "The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.",

keywords = "Anagostic interaction, C-H activation, Carbonyl ligands, Phosphines, Rhodium",

author = "Michael Montag and Irena Efremenko and Revital Cohen and Gregory Leitus and Shimon, {Linda J.W.} and Yael Diskin-Posner and Yehoshoa Ben-David and Martin, {Jan M.L.} and David Milstein",

year = "2008",

month = sep,

day = "19",

doi = "10.1002/chem.200801171",

language = "אנגלית",

volume = "14",

pages = "8183--8194",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "27",

}

Montag, M, Efremenko, I, Cohen, R, Leitus, G, Shimon, LJW, Diskin-Posner, Y, Ben-David, Y, Martin, JML & Milstein, D 2008, 'The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)₂(phosphine)₂]⁺: An experimental and theoretical examination', Chemistry - A European Journal, vol. 14, no. 27, pp. 8183-8194. https://doi.org/10.1002/chem.200801171

TY - JOUR

T1 - The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+

T2 - An experimental and theoretical examination

AU - Montag, Michael

AU - Efremenko, Irena

AU - Cohen, Revital

AU - Leitus, Gregory

AU - Shimon, Linda J.W.

AU - Diskin-Posner, Yael

AU - Ben-David, Yehoshoa

AU - Martin, Jan M.L.

AU - Milstein, David

PY - 2008/9/19

Y1 - 2008/9/19

N2 - The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.

AB - The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.

KW - Anagostic interaction

KW - C-H activation

KW - Carbonyl ligands

KW - Phosphines

KW - Rhodium

UR - http://www.scopus.com/inward/record.url?scp=53849087194&partnerID=8YFLogxK

U2 - 10.1002/chem.200801171

DO - 10.1002/chem.200801171

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

AN - SCOPUS:53849087194

SN - 0947-6539

VL - 14

SP - 8183

EP - 8194

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 27

ER -

The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)₂(phosphine)₂]⁺: An experimental and theoretical examination

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this