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]

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.

doi:10.1021/acs.inorgchem.6b02372

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]

Journal Article · Sun Dec 11 23:00:00 EST 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b02372· OSTI ID:1342963

Baddour, Frederick G. ^[1]; Hyre, Ariel S. ^[1]; Guillet, Jesse L. ^[1]; Pascual, David ^[2]; Lopez-de-Luzuriaga, Jose Maria ^[2]; Alam, Todd M. ^[3]; Bacon, Jeffrey W. ^[1]; ^[1]

Boston Univ., Boston, MA (United States)
Univ. de La Rioja, Logrono (Spain)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: NSF

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1342963

Report Number(s):: SAND--2016-10492J; 648393

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 56; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Reactivity of [M(C∧P)(acac-O,O‘)] [M = Pt, Pd; C∧P = CH ₂ -C ₆ H ₄ -P( o -tolyl) ₂ -κC,P; acac = 2,4-pentanedionato] toward HgX ₂ (X = Br, I, CH ₃ COO, CF ₃ COO). New Polynuclear Complexes Containing Pt−Hg Bonds. Molecular Structures of [{Pt(C∧P)(acac-O,O‘)- HgBr(μ-Br)} ₂ (μ-HgBr ₂ )], an Unprecedented Square-Planar Bromomercurate Complex, and [{Pt(C∧P)(μ-O ₂ CCH ₃ ) ₂ Hg(μ ³ -acac ² ^- -κC ³ ,O)Hg(O ₂ CCH ₃ -κO)}· CHCl ₃ ] ₂ , the First Complex Containing Asymmetric Dimercurated Acetylacetone Ara, Irene; Falvello, Larry R.; Forniés, Juan Organometallics, Vol. 19, Issue 16 https://doi.org/10.1021/om000223y	journal	July 2000
Complexes with unbridged dative bonds between osmium and a Group 6 element. Structures of (OC)5-x(tert-BuNC)xOsCr(CO)5 (x = 1, 2) Shipley, John A.; Batchelor, Raymond J.; Einstein, Frederick W. B. Organometallics, Vol. 10, Issue 10 https://doi.org/10.1021/om00056a037	journal	October 1991
Crystal structure and molecular geometry of a square-pyramidal platinum(II) complex [{2,6-(Me2NCH2)2C6H3}Pt(.mu.-{(p-tol)NC(H)N(i-Pr)})HgBrCl] containing a PtII-to-HgII donor bond Van der Ploeg, Antonius F. M. J.; Van Koten, Gerard; Vrieze, Kees Organometallics, Vol. 1, Issue 8 https://doi.org/10.1021/om00068a013	journal	August 1982
Steric and Solvent Effects on the CO ₂ Fixation of Magnesium Compounds Yang, Kuo-Ching; Chang, Chung-Cheng; Yeh, Charng-Sheng Organometallics, Vol. 20, Issue 1 https://doi.org/10.1021/om000735c	journal	January 2001
Heteropolynuclear Pt(II)–M(I) Clusters with a C ^∧ N ^∧ C Biscyclometalated Ligand Fuertes, Sara; Woodall, Christopher H.; Raithby, Paul R. Organometallics, Vol. 31, Issue 11 https://doi.org/10.1021/om300170j	journal	May 2012
Heterobimetallic Complexes with Polar, Unsupported Cu–Fe and Zn–Fe Bonds Stabilized by N-Heterocyclic Carbenes Jayarathne, Upul; Mazzacano, Thomas J.; Bagherzadeh, Sharareh Organometallics, Vol. 32, Issue 14 https://doi.org/10.1021/om400471u	journal	July 2013
Investigation of the Electronic Structure of Mono(1,1′-Diamidoferrocene) Uranium(IV) Complexes Duhović, Selma; Oria, Jeremy V.; Odoh, Samuel O. Organometallics, Vol. 32, Issue 20 https://doi.org/10.1021/om400521k	journal	August 2013
Evaluation of the σ-Donation from Group 11 Metals (Cu, Ag, Au) to Silane, Germane, and Stannane Based on the Experimental/Theoretical Systematic Approach Kameo, Hajime; Kawamoto, Tatsuya; Bourissou, Didier Organometallics, Vol. 34, Issue 8 https://doi.org/10.1021/om501159v	journal	April 2015
Guilty on Two Counts: Stepwise Coordination of Two Fluoride Anions to the Antimony Atom of a Noninnocent Stibine Ligand Jones, James S.; Wade, Casey R.; Gabbaı̈, François P. Organometallics, Vol. 34, Issue 11 https://doi.org/10.1021/om501291g	journal	November 2014
Complexes Containing Unbridged Dative Metal−Metal Bonds and the Strong Acceptor Ru(CO) ₃ (SiCl ₃ ) ₂ Moiety. Comments on the Transition Metal to Silicon Bond Jiang, Faming; Male, Jonathan L.; Biradha, Kumar Organometallics, Vol. 17, Issue 26 https://doi.org/10.1021/om980116s	journal	December 1998
Compounds with Unbridged Dative Metal−Metal Bonds of Formula (R ₃ P) ₂ (OC) ₃ OsW(CO) ₅ and Related Complexes Jiang, Faming; Jenkins, Hilary A.; Biradha, Kumar Organometallics, Vol. 19, Issue 24 https://doi.org/10.1021/om990790p	journal	November 2000
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Mixed nickel co-ordination in a binuclear complex with a short nickel–nickel bond Bonamico, M.; Dessy, G.; Fares, V. J. Chem. Soc. D, Vol. 0, Issue 13 https://doi.org/10.1039/C29690000697	journal	January 1969
Metal-only Lewis pairs featuring unsupported Pt→M (M = Zn or Cd) dative bonds Ma, Mengtao; Sidiropoulos, Anastas; Ralte, Lalrempuia Chem. Commun., Vol. 49, Issue 1 https://doi.org/10.1039/C2CC37442K	journal	January 2013
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Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtCCCCCCCC] _m PtX segments; iterative syntheses and functionalization for measurements of single molecule properties Zheng, Qinglin; Schneider, Jakob F.; Amini, Hashem Dalton Transactions, Vol. 48, Issue 17 https://doi.org/10.1039/c9dt00870e	journal	January 2019

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