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Title: Pt–Mg, Pt–Ca, and Pt–Zn lantern complexes and metal-only donor–acceptor interactions [Pt-Mg Pt-Ca and Pt-Zn compounds with metal-only donor-acceptor interactions]

Abstract

Here, Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR) 4(L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal–metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc) 4(OH 2)] (1), [PtMg(tba) 4(OH 2)] (2), [PtCa(tba) 4(OH 2)] (3), [PtZn(tba) 4(OH 2)] (4), and a mononuclear control (Ph 4P) 2[Pt(SAc) 4] (5) have been synthesized. Crystallographic data show close Pt–M contacts enforced by the lantern structure in each dinuclear case. 195Pt-NMR spectroscopy of 1–4, (Ph 4P) 2[Pt(SAc) 4] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH 3 (thioacetate, SAc), C 6H 5 (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc) 4(OH 2)], and computational studies demonstrate significant dative character. In all of 1–4, the short Pt–M distances suggest that metal-only Lewis donor (Pt)–Lewis acceptormore » (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic.« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [1]; ORCiD logo [1]
  1. Boston Univ., Boston, MA (United States)
  2. Univ. de La Rioja, Logrono (Spain)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1342963
Report Number(s):
SAND-2016-10492J
Journal ID: ISSN 0020-1669; 648393
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 1; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Baddour, Frederick G., Hyre, Ariel S., Guillet, Jesse L., Pascual, David, Lopez-de-Luzuriaga, Jose Maria, Alam, Todd M., Bacon, Jeffrey W., and Doerrer, Linda H. Pt–Mg, Pt–Ca, and Pt–Zn lantern complexes and metal-only donor–acceptor interactions [Pt-Mg Pt-Ca and Pt-Zn compounds with metal-only donor-acceptor interactions]. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b02372.
Baddour, Frederick G., Hyre, Ariel S., Guillet, Jesse L., Pascual, David, Lopez-de-Luzuriaga, Jose Maria, Alam, Todd M., Bacon, Jeffrey W., & Doerrer, Linda H. Pt–Mg, Pt–Ca, and Pt–Zn lantern complexes and metal-only donor–acceptor interactions [Pt-Mg Pt-Ca and Pt-Zn compounds with metal-only donor-acceptor interactions]. United States. doi:10.1021/acs.inorgchem.6b02372.
Baddour, Frederick G., Hyre, Ariel S., Guillet, Jesse L., Pascual, David, Lopez-de-Luzuriaga, Jose Maria, Alam, Todd M., Bacon, Jeffrey W., and Doerrer, Linda H. Mon . "Pt–Mg, Pt–Ca, and Pt–Zn lantern complexes and metal-only donor–acceptor interactions [Pt-Mg Pt-Ca and Pt-Zn compounds with metal-only donor-acceptor interactions]". United States. doi:10.1021/acs.inorgchem.6b02372. https://www.osti.gov/servlets/purl/1342963.
@article{osti_1342963,
title = {Pt–Mg, Pt–Ca, and Pt–Zn lantern complexes and metal-only donor–acceptor interactions [Pt-Mg Pt-Ca and Pt-Zn compounds with metal-only donor-acceptor interactions]},
author = {Baddour, Frederick G. and Hyre, Ariel S. and Guillet, Jesse L. and Pascual, David and Lopez-de-Luzuriaga, Jose Maria and Alam, Todd M. and Bacon, Jeffrey W. and Doerrer, Linda H.},
abstractNote = {Here, Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR)4(L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal–metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc)4(OH2)] (1), [PtMg(tba)4(OH2)] (2), [PtCa(tba)4(OH2)] (3), [PtZn(tba)4(OH2)] (4), and a mononuclear control (Ph4P)2[Pt(SAc)4] (5) have been synthesized. Crystallographic data show close Pt–M contacts enforced by the lantern structure in each dinuclear case. 195Pt-NMR spectroscopy of 1–4, (Ph4P)2[Pt(SAc)4] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH3 (thioacetate, SAc), C6H5 (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc)4(OH2)], and computational studies demonstrate significant dative character. In all of 1–4, the short Pt–M distances suggest that metal-only Lewis donor (Pt)–Lewis acceptor (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic.},
doi = {10.1021/acs.inorgchem.6b02372},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 1,
volume = 56,
place = {United States},
year = {2016},
month = {12}
}

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Works referencing / citing this record:

CCDC 1530242: Experimental Crystal Structure Determination: JANCEJ : tetrakis(μ-thiobenzoato)-aqua-magnesium-platinum dichloromethane solvate
dataset, January 2017

  • Baddour, Frederick G.; Hyre, Ariel S.; Guillet, Jesse L.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1ncbn0

CCDC 1530243: Experimental Crystal Structure Determination: JANCIN : octakis(μ-thiobenzoato)-diaqua-di-calcium-di-platinum dichloromethane solvate dihydrate
dataset, January 2017

  • Baddour, Frederick G.; Hyre, Ariel S.; Guillet, Jesse L.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1ncbp1

CCDC 1530244: Experimental Crystal Structure Determination: JANCOT : octakis(μ-thiobenzoato)-diaqua-di-platinum-di-zinc tetrahydrofuran solvate
dataset, January 2017

  • Baddour, Frederick G.; Hyre, Ariel S.; Guillet, Jesse L.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1ncbq2

CCDC 1530245: Experimental Crystal Structure Determination: JANCUZ : bis(tetraphenylphosphonium) tetrakis(thioacetato)-platinum(ii) hydrate
dataset, January 2017