Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes: A neglected ligand species

Lars Arne Schaper, Xuhui Wei, Philipp J. Altmann, Karl Öfele, Alexander Pöthig, Markus Drees, J. Mink, Eberhardt Herdtweck, Bettina Bechlars, Wolfgang A. Herrmann, Fritz E. Kühn

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of "normal" tetrazolylidenes (1,4-substitution pattern) and "abnormal" tetrazolylidenes (also referred to as "mesoionic carbenes"; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.

Original languageEnglish
Pages (from-to)7031-7044
Number of pages14
JournalInorganic Chemistry
Volume52
Issue number12
DOIs
Publication statusPublished - Jun 17 2013

Fingerprint

Coordination Complexes
carbenes
Transition metals
Substitution reactions
transition metals
substitutes
Ligands
ligands
synthesis
X ray crystallography
spectroscopy
Nuclear magnetic resonance spectroscopy
crystallography
reagents
Raman spectroscopy
Infrared spectroscopy
nuclear magnetic resonance
causes
carbene
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Schaper, L. A., Wei, X., Altmann, P. J., Öfele, K., Pöthig, A., Drees, M., ... Kühn, F. E. (2013). Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes: A neglected ligand species. Inorganic Chemistry, 52(12), 7031-7044. https://doi.org/10.1021/ic4005449

Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes : A neglected ligand species. / Schaper, Lars Arne; Wei, Xuhui; Altmann, Philipp J.; Öfele, Karl; Pöthig, Alexander; Drees, Markus; Mink, J.; Herdtweck, Eberhardt; Bechlars, Bettina; Herrmann, Wolfgang A.; Kühn, Fritz E.

In: Inorganic Chemistry, Vol. 52, No. 12, 17.06.2013, p. 7031-7044.

Research output: Contribution to journalArticle

Schaper, LA, Wei, X, Altmann, PJ, Öfele, K, Pöthig, A, Drees, M, Mink, J, Herdtweck, E, Bechlars, B, Herrmann, WA & Kühn, FE 2013, 'Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes: A neglected ligand species', Inorganic Chemistry, vol. 52, no. 12, pp. 7031-7044. https://doi.org/10.1021/ic4005449
Schaper, Lars Arne ; Wei, Xuhui ; Altmann, Philipp J. ; Öfele, Karl ; Pöthig, Alexander ; Drees, Markus ; Mink, J. ; Herdtweck, Eberhardt ; Bechlars, Bettina ; Herrmann, Wolfgang A. ; Kühn, Fritz E. / Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes : A neglected ligand species. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 12. pp. 7031-7044.
@article{29fcafffb6f7444e9161753821762997,
title = "Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes: A neglected ligand species",
abstract = "To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of {"}normal{"} tetrazolylidenes (1,4-substitution pattern) and {"}abnormal{"} tetrazolylidenes (also referred to as {"}mesoionic carbenes{"}; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.",
author = "Schaper, {Lars Arne} and Xuhui Wei and Altmann, {Philipp J.} and Karl {\"O}fele and Alexander P{\"o}thig and Markus Drees and J. Mink and Eberhardt Herdtweck and Bettina Bechlars and Herrmann, {Wolfgang A.} and K{\"u}hn, {Fritz E.}",
year = "2013",
month = "6",
day = "17",
doi = "10.1021/ic4005449",
language = "English",
volume = "52",
pages = "7031--7044",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes

T2 - A neglected ligand species

AU - Schaper, Lars Arne

AU - Wei, Xuhui

AU - Altmann, Philipp J.

AU - Öfele, Karl

AU - Pöthig, Alexander

AU - Drees, Markus

AU - Mink, J.

AU - Herdtweck, Eberhardt

AU - Bechlars, Bettina

AU - Herrmann, Wolfgang A.

AU - Kühn, Fritz E.

PY - 2013/6/17

Y1 - 2013/6/17

N2 - To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of "normal" tetrazolylidenes (1,4-substitution pattern) and "abnormal" tetrazolylidenes (also referred to as "mesoionic carbenes"; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.

AB - To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of "normal" tetrazolylidenes (1,4-substitution pattern) and "abnormal" tetrazolylidenes (also referred to as "mesoionic carbenes"; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.

UR - http://www.scopus.com/inward/record.url?scp=84879232030&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84879232030&partnerID=8YFLogxK

U2 - 10.1021/ic4005449

DO - 10.1021/ic4005449

M3 - Article

C2 - 23706110

AN - SCOPUS:84879232030

VL - 52

SP - 7031

EP - 7044

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 12

ER -