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Title: Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex

Abstract

A dicopper complex featuring a symmetrically bridging nitrile ligand and supported by a binucleating naphthyridine-based ligand, [Cu2(μ-η11-MeCN)DPFN](NTf2)2, was treated with phosphaalkynes (RC$$\equiv$$P, isoelectronic analogues of nitriles) to yield dicopper complexes that exhibit phosphaalkynes in rare μ-η22 binding coordination modes. X-ray crystallography revealed that these unusual “tilted” structures exist in two isomeric forms (R “up” vs. R “sideways”), depending on the steric profile of the phosphaalkyne's alkyl group (R = Me, Ad, or tBu). Only one isomer is observed in both solution and the solid state for R = Me (sideways) and tBu (up). With intermediate steric bulk (R = Ad), the energy difference between the two geometries is small enough that both are observed in solution, and NMR spectroscopy and computations indicate that the solid-state structure corresponds to the minor isomer observed in solution. Meanwhile, treatment of [Cu2(μ-η11-MeCN)DPFN](NTf2)2 with 2-butyne affords [Cu2(μ-η22-(MeC$$\equiv$$CMe))DPFN](NTf2)2: its similar ligand geometry demonstrates that the tilted μ-η22 binding mode is not limited to phosphaalkynes but reflects a more general trend, which can be rationalized via an NBO analysis showing maximization of π-backbonding.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Univ. Regensburg, Regensburg (Germany). Inst. für Anorganische Chemie
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH); Alexander von Humboldt Foundation; National Science Foundation (NSF)
OSTI Identifier:
1581662
Alternate Identifier(s):
OSTI ID: 1615295
Grant/Contract Number:  
AC02-05CH11231; S10-RR027172; S10OD023532; DGE 1106400; SRR023679A; 1S10RR016634-01; GM68933
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nicolay, Amélie, Ziegler, Micah S., Small, David W., Grünbauer, Rebecca, Scheer, Manfred, and Tilley, T. Don. Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex. United States: N. p., 2020. Web. doi:10.1039/c9sc05835d.
Nicolay, Amélie, Ziegler, Micah S., Small, David W., Grünbauer, Rebecca, Scheer, Manfred, & Tilley, T. Don. Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex. United States. https://doi.org/10.1039/c9sc05835d
Nicolay, Amélie, Ziegler, Micah S., Small, David W., Grünbauer, Rebecca, Scheer, Manfred, and Tilley, T. Don. Wed . "Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex". United States. https://doi.org/10.1039/c9sc05835d.
@article{osti_1581662,
title = {Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex},
author = {Nicolay, Amélie and Ziegler, Micah S. and Small, David W. and Grünbauer, Rebecca and Scheer, Manfred and Tilley, T. Don},
abstractNote = {A dicopper complex featuring a symmetrically bridging nitrile ligand and supported by a binucleating naphthyridine-based ligand, [Cu2(μ-η1:η1-MeCN)DPFN](NTf2)2, was treated with phosphaalkynes (RC$\equiv$P, isoelectronic analogues of nitriles) to yield dicopper complexes that exhibit phosphaalkynes in rare μ-η2:η2 binding coordination modes. X-ray crystallography revealed that these unusual “tilted” structures exist in two isomeric forms (R “up” vs. R “sideways”), depending on the steric profile of the phosphaalkyne's alkyl group (R = Me, Ad, or tBu). Only one isomer is observed in both solution and the solid state for R = Me (sideways) and tBu (up). With intermediate steric bulk (R = Ad), the energy difference between the two geometries is small enough that both are observed in solution, and NMR spectroscopy and computations indicate that the solid-state structure corresponds to the minor isomer observed in solution. Meanwhile, treatment of [Cu2(μ-η1:η1-MeCN)DPFN](NTf2)2 with 2-butyne affords [Cu2(μ-η2:η2-(MeC$\equiv$CMe))DPFN](NTf2)2: its similar ligand geometry demonstrates that the tilted μ-η2:η2 binding mode is not limited to phosphaalkynes but reflects a more general trend, which can be rationalized via an NBO analysis showing maximization of π-backbonding.},
doi = {10.1039/c9sc05835d},
journal = {Chemical Science},
number = 6,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}

Journal Article:
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https://doi.org/10.1039/c9sc05835d

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