A Scandium–Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4–
Abstract
Abstract The first example of the OCPPCO ligand, diisophosphaethynolate, is reported via reductive coupling of a Sc−OCP precursor. Upon reduction with KC 8 , isolation of the dinuclear complex, namely [K(OEt 2 )] 2 [(nacnac)Sc(OAr)] 2 (OCPPCO), is observed, leading to a unique motif [OCPPCO] 4− , stabilized by two scandium centers. Detailed NMR spectra of all complexes as well as IR and single crystal X‐ray studies were obtained to fully elucidate the nature of these complexes in solution as well as in the solid state. Theory is combined to probe the electronic structure and orbitals responsible for the bonding interactions in the Sc−OCPPCO−Sc skeleton but also to compare to the linear mode observed in the precursor.
- Authors:
-
[1];
[1]
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Vrije Univ. Brussel (Belgium)
- ETH Zürich (Switzerland)
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
- OSTI Identifier:
- 1843646
- Alternate Identifier(s):
- OSTI ID: 1414601
- Grant/Contract Number:
- SC0012486; DEFG02-07ER15893
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 4; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, and Mindiola, Daniel J. A Scandium–Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4–. United States: N. p., 2017.
Web. doi:10.1002/anie.201710757.
Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, & Mindiola, Daniel J. A Scandium–Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4–. United States. https://doi.org/10.1002/anie.201710757
Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, and Mindiola, Daniel J. Wed .
"A Scandium–Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4–". United States. https://doi.org/10.1002/anie.201710757. https://www.osti.gov/servlets/purl/1843646.
@article{osti_1843646,
title = {A Scandium–Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4–},
author = {Grant, Lauren N. and Pinter, Balazs and Manor, Brian C. and Grützmacher, Hansjörg and Mindiola, Daniel J.},
abstractNote = {Abstract The first example of the OCPPCO ligand, diisophosphaethynolate, is reported via reductive coupling of a Sc−OCP precursor. Upon reduction with KC 8 , isolation of the dinuclear complex, namely [K(OEt 2 )] 2 [(nacnac)Sc(OAr)] 2 (OCPPCO), is observed, leading to a unique motif [OCPPCO] 4− , stabilized by two scandium centers. Detailed NMR spectra of all complexes as well as IR and single crystal X‐ray studies were obtained to fully elucidate the nature of these complexes in solution as well as in the solid state. Theory is combined to probe the electronic structure and orbitals responsible for the bonding interactions in the Sc−OCPPCO−Sc skeleton but also to compare to the linear mode observed in the precursor.},
doi = {10.1002/anie.201710757},
journal = {Angewandte Chemie (International Edition)},
number = 4,
volume = 57,
place = {United States},
year = {Wed Nov 29 00:00:00 EST 2017},
month = {Wed Nov 29 00:00:00 EST 2017}
}
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Works referenced in this record:
Is the phosphaethynolate anion, (OCP)−, an ambident nucleophile? A spectroscopic and computational study
journal, January 2014
- Heift, Dominikus; Benkő, Zoltán; Grützmacher, Hansjörg
- Dalton Transactions, Vol. 43, Issue 15
Does Diisooxocyan (OCN−NCO) Exist?
journal, January 1996
- Schulz, Axel; Klapötke, Thomas M.
- Inorganic Chemistry, Vol. 35, Issue 16
The 2-Phosphaethynolate Anion: A Convenient Synthesis and [2+2] Cycloaddition Chemistry
journal, August 2013
- Jupp, Andrew R.; Goicoechea, Jose M.
- Angewandte Chemie International Edition, Vol. 52, Issue 38
Phosphanierung von Kohlenmonoxid: eine einfache Synthese von Natriumphosphaethinolat (NaOCP)
journal, July 2011
- Puschmann, Florian Frank; Stein, Daniel; Heift, Dominikus
- Angewandte Chemie, Vol. 123, Issue 36
Phosphideinbau in ein Cyclotrisilen
journal, November 2014
- Robinson, Thomas P.; Cowley, Michael J.; Scheschkewitz, David
- Angewandte Chemie, Vol. 127, Issue 2
Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex
journal, March 2017
- Xiong, Yun; Yao, Shenglai; Szilvási, Tibor
- Angewandte Chemie, Vol. 129, Issue 15
The 2-Phosphaethynolate Anion: A Convenient Synthesis and [2+2] Cycloaddition Chemistry
journal, August 2013
- Jupp, Andrew R.; Goicoechea, Jose M.
- Angewandte Chemie, Vol. 125, Issue 38
Synthesis of P 2 C 2 O 2 and P 2 CO via NHC-mediated coupling of the phosphaethynolate anion
journal, January 2017
- Gilliard, Robert J.; Suter, Riccardo; Schrader, Erik
- Chemical Communications, Vol. 53, Issue 91
Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX – (E = As, P, and N; X = S and O) Anions
journal, June 2017
- Hou, Gao-Lei; Chen, Bo; Transue, Wesley J.
- Journal of the American Chemical Society, Vol. 139, Issue 26
A Planar Ti 2 P 2 Core Assembled by Reductive Decarbonylation of − O−C≡P and P−P Radical Coupling
journal, April 2017
- Grant, Lauren N.; Pinter, Balazs; Manor, Brian C.
- Chemistry - A European Journal, Vol. 23, Issue 26
From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene
journal, March 2016
- Yao, Shenglai; Xiong, Yun; Szilvási, Tibor
- Angewandte Chemie, Vol. 128, Issue 15
Synthesis and Characterization of Terminal [Re(XCO)(CO) 2 (triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes
journal, September 2012
- Alidori, Simone; Heift, Dominikus; Santiso-Quinones, Gustavo
- Chemistry - A European Journal, Vol. 18, Issue 46
Uranium and thorium complexes of the phosphaethynolate ion
journal, January 2015
- Camp, Clément; Settineri, Nicholas; Lefèvre, Julia
- Chemical Science, Vol. 6, Issue 11
Phosphination of Carbon Monoxide: A Simple Synthesis of Sodium Phosphaethynolate (NaOCP)
journal, July 2011
- Puschmann, Florian Frank; Stein, Daniel; Heift, Dominikus
- Angewandte Chemie International Edition, Vol. 50, Issue 36
Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex
journal, March 2017
- Xiong, Yun; Yao, Shenglai; Szilvási, Tibor
- Angewandte Chemie International Edition, Vol. 56, Issue 15
Formation of a Uranium-Bound η 1 -Cyaphide (CP – ) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP – )
journal, October 2017
- Hoerger, Christopher J.; Heinemann, Frank W.; Louyriac, Elisa
- Organometallics, Vol. 36, Issue 22
A nucleophilic niobium(V) nitride prepared by isocyanate decarbonylation
journal, January 1997
- G. Fickes, Michael; L. Odom, Aaron; C. Cummins, Christopher
- Chemical Communications, Issue 20
From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene
journal, March 2016
- Yao, Shenglai; Xiong, Yun; Szilvási, Tibor
- Angewandte Chemie International Edition, Vol. 55, Issue 15
Phosphide Delivery to a Cyclotrisilene
journal, November 2014
- Robinson, Thomas P.; Cowley, Michael J.; Scheschkewitz, David
- Angewandte Chemie International Edition, Vol. 54, Issue 2
Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation
journal, January 2017
- Joost, Maximilian; Transue, Wesley J.; Cummins, Christopher C.
- Chemical Communications, Vol. 53, Issue 77
Isolation of Au-, Co-η 1 PCO and Cu-η 2 PCO complexes, conversion of an Ir–η 1 PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion
journal, January 2016
- Liu, Liu; Ruiz, David A.; Dahcheh, Fatme
- Chemical Science, Vol. 7, Issue 3
Isolation of a Heavier Cyclobutadiene Analogue: 2,4-Digerma-1,3-diphosphacyclobutadiene
journal, May 2016
- Wu, Yile; Liu, Liu; Su, Jue
- Organometallics, Vol. 35, Issue 11