Tetracopper σ‐Bound μ ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Ríos, Pablo; See, Matthew S.; Handford, Rex C.; Cooper, Jason K.; Don Tilley, T.

doi:10.1002/anie.202310307

Tetracopper σ‐Bound μ ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Journal Article · Wed Sep 27 00:00:00 EDT 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202310307· OSTI ID:2006704

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Instituto de Investigaciones Químicas (IIQ) Departamento de Química Inorgánica Centro de Innovación en Química Avanzada (ORFEO-CINQA) CSIC and Universidad de Sevilla 41092 Sevilla Spain, Department of Chemistry University of California Berkeley USA
Department of Chemistry University of California Berkeley USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Department of Chemistry University of California Berkeley USA
Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract

Reactions of a dicopper(I) tert ‐butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ ‐acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. These compounds possess an unusual μ ₄ ‐ η ¹ : η ¹ : η ¹ : η ¹ coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal‐metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne‐containing clusters.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2006704

Alternate ID(s):: OSTI ID: 2203996
OSTI ID: 2280922

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 45 Vol. 62; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (30)

Self-Assembly of Copper Acetylide Molecules into Extremely Thin Nanowires and Nanocables Judai, K.; Nishijo, J.; Nishi, N. Advanced Materials, Vol. 18, Issue 21 https://doi.org/10.1002/adma.200600771	journal	November 2006
Synthesis, Structure, Photophysics, and Excited-State Redox Properties of the Novel Luminescent Tetranuclear Acetylidocopper(I) Complex[Cu4(μ-dppm)4(μ4-η1,η2-CC-)](BF4)2 Yam, Vivian Wing-Wah; Fung, Wendy Kit-Mai; Cheung, Kung-Kai Angewandte Chemie International Edition in English, Vol. 35, Issue 10 https://doi.org/10.1002/anie.199611001	journal	June 1996
Temperature-Mediated Template Release: Facile Growth of Copper(I) Mixed Ethynediide/Isopropylethynide Nanoclusters Zhang, Leon Li-Min; Mak, Thomas C. W. Angewandte Chemie International Edition, Vol. 56, Issue 51 https://doi.org/10.1002/anie.201708760	journal	November 2017
A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes Desnoyer, Addison N.; Nicolay, Amélie; Ziegler, Micah S. Angewandte Chemie International Edition, Vol. 59, Issue 31 https://doi.org/10.1002/anie.202004346	journal	May 2020
Structure Determination of Homoleptic AuI, AgI, and CuI Aryl/Alkylethynyl Coordination Polymers by X-ray Powder Diffraction Chui, Stephen S. Y.; Ng, Miro F. Y.; Che, Chi-Ming Chemistry - A European Journal, Vol. 11, Issue 6 https://doi.org/10.1002/chem.200400881	journal	March 2005
Cuprophilic Interactions in and between Molecular Entities Harisomayajula, N. V. Satyachand; Makovetskyi, Serhii; Tsai, Yi‐Chou Chemistry – A European Journal, Vol. 25, Issue 38 https://doi.org/10.1002/chem.201900332	journal	May 2019
Walter Reppe Revival – Identification and Genesis of Copper Acetylides Cu₂C₂ as Active Species in Ethynylation Reactions Bruhm, Tobias; Abram, Andrea; Häusler, Johannes Chemistry – A European Journal, Vol. 27, Issue 68 https://doi.org/10.1002/chem.202101932	journal	August 2021
High-resolution Raman spectra of acetylene, acetylene-d1, and acetylene-d2 Fast, H.; Welsh, H. L. Journal of Molecular Spectroscopy, Vol. 41, Issue 1 https://doi.org/10.1016/0022-2852(72)90133-6	journal	January 1972
Coordination complexes exhibiting room-temperature phosphorescence: Evaluation of their suitability as triplet emitters in organic light emitting diodes Evans, Rachel C.; Douglas, Peter; Winscom, Christopher J. Coordination Chemistry Reviews, Vol. 250, Issue 15-16 https://doi.org/10.1016/j.ccr.2006.02.007	journal	August 2006
Homoleptic transition metal acetylides Buschbeck, Roy; Low, Paul J.; Lang, Heinrich Coordination Chemistry Reviews, Vol. 255, Issue 1-2 https://doi.org/10.1016/j.ccr.2010.07.004	journal	January 2011
Recent progress in functional atom-precise coinage metal clusters protected by alkynyl ligands Zhang, Miao-Miao; Dong, Xi-Yan; Wang, Ya-Jie Coordination Chemistry Reviews, Vol. 453 https://doi.org/10.1016/j.ccr.2021.214315	journal	February 2022
Bimetallics in a Nutshell: Complexes Supported by Chelating Naphthyridine-Based Ligands Desnoyer, Addison N.; Nicolay, Amélie; Rios, Pablo Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00382	journal	September 2020
Molecular Design of Transition Metal Alkynyl Complexes as Building Blocks for Luminescent Metal-Based Materials: Structural and Photophysical Aspects Yam, Vivian Wing-Wah Accounts of Chemical Research, Vol. 35, Issue 7 https://doi.org/10.1021/ar0000758	journal	May 2002
Luminescent μ-Ethynediyl and μ-Butadiynediyl Binuclear Gold(I) Complexes: Observation of ³(ππ*) Emissions from Bridging C_n²^- Units Che, Chi-Ming; Chao, Hsiu-Yi; Miskowski, Vincent M. Journal of the American Chemical Society, Vol. 123, Issue 21 https://doi.org/10.1021/ja001706w	journal	May 2001
Silver(I) 1,3-Butadiynediide and Two Related Silver(I) Double Salts Containing the C₄^2- Dianion Zhao, Liang; Mak, Thomas C. W. Journal of the American Chemical Society, Vol. 126, Issue 22 https://doi.org/10.1021/ja049772b	journal	May 2004
A Dicopper Nitrenoid by Oxidation of a Cu ^I Cu ^I Core: Synthesis, Electronic Structure, and Reactivity Desnoyer, Addison N.; Nicolay, Amélie; Ziegler, Micah S. Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c02235	journal	April 2021
Dicopper Cu(I)Cu(I) and Cu(I)Cu(II) Complexes in Copper-Catalyzed Azide–Alkyne Cycloaddition Ziegler, Micah S.; Lakshmi, K. V.; Tilley, T. Don Journal of the American Chemical Society, Vol. 139, Issue 15 https://doi.org/10.1021/jacs.6b13261	journal	April 2017
“Doping” of Polyyne with an Organometallic Fragment Leads to Highly Conductive Metallapolyyne Molecular Wire Tanaka, Yuya; Kato, Yuya; Tada, Tomofumi Journal of the American Chemical Society, Vol. 140, Issue 32 https://doi.org/10.1021/jacs.8b04484	journal	July 2018
Synthesis of Water-Soluble Poly(p-phenyleneethynylene) in Neat Water under Aerobic Conditions via Suzuki-Miyaura Polycondensation Using a Diborylethyne Synthon Kang, Youn K.; Deria, Pravas; Carroll, Patrick J. Organic Letters, Vol. 10, Issue 7 https://doi.org/10.1021/ol702758f	journal	March 2008
Alkynylcopper(I) Complexes with PPh3 Ligands. Preparation, Structure, and Alkyne Ligand Transfer to Palladium(II) Complexes Osakada, Kohtaro; Takizawa, Tadashi; Yamamoto, Takakazu Organometallics, Vol. 14, Issue 7 https://doi.org/10.1021/om00007a061	journal	July 1995
Cyclopentadienyl and Alkynyl Copper(I ) Derivatives with the [{Ti(η 5 -C 5 Me 5 )(μ-NH)} 3 (μ 3 -N)] Metalloligand Martínez-Espada, Noelia; Mena, Miguel; Mosquera, Marta E. G. Organometallics, Vol. 29, Issue 24 https://doi.org/10.1021/om100824q	journal	December 2010
Copper(I) Alkyne and Alkynide Complexes Lang, Heinrich; Jakob, Alexander; Milde, Bianca Organometallics, Vol. 31, Issue 22 https://doi.org/10.1021/om300628g	journal	August 2012
Restoration of catalytic activity by the preservation of ligand structure: Cu-catalysed asymmetric conjugate addition with 1,1-diborylmethane Kim, Changhee; Roh, Byeongdo; Lee, Hong Geun Chemical Science, Vol. 12, Issue 10 https://doi.org/10.1039/D0SC06543A	journal	January 2021
Robust dicopper(i) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand Ríos, Pablo; See, Matthew S.; Handford, Rex C. Chemical Science, Vol. 13, Issue 22 https://doi.org/10.1039/D2SC00848C	journal	January 2022
A novel luminescent copper(i) complex containing an acetylenediide-bridged, butterfly-shaped tetranuclear core Song, Hai-Bin; Wang, Quan-Ming; Mak, Thomas C. W. Chemical Communications, Issue 17 https://doi.org/10.1039/b102717b	journal	January 2001
An oscillating C22? unit inside a copper rectangleElectronic supplementary information (ESI) available: NMR spectra and computational details. See http://www.rsc.org/suppdata/cc/b3/b301842c/ Lo, Wing-Yin; Lam, Chi-Ho; Fung, Wendy Kit-Mai Chemical Communications, Issue 11 https://doi.org/10.1039/b301842c	journal	January 2003
CH/? hydrogen bonds in crystals Nishio, Motohiro CrystEngComm, Vol. 6, Issue 27 https://doi.org/10.1039/b313104a	journal	January 2004
Covalent radii revisited Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E. Dalton Transactions, Issue 21 https://doi.org/10.1039/b801115j	journal	January 2008
Comparison of the experimental, semi-experimental and ab initio equilibrium structures of acetylene: Influence of relativisitic effects and of the diagonal Born–Oppenheimer corrections Liévin, J.; Demaison, J.; Herman, M. The Journal of Chemical Physics, Vol. 134, Issue 6 https://doi.org/10.1063/1.3553203	journal	February 2011
Structures of cubic and orthorhombic phases of acetylene by single-crystal neutron diffraction McMullan, R. K.; Kvick, Å ;.; Popelier, P. Acta Crystallographica Section B Structural Science, Vol. 48, Issue 5 https://doi.org/10.1107/S0108768192004774	journal	October 1992

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Tetracopper σ‐Bound μ ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Journal Article · Wed Sep 27 00:00:00 EDT 2023 · Angewandte Chemie · OSTI ID:2006714

Tetracopper σ‐Bound μ ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

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