Sage Journals: Discover world-class research

Abstract

Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu₂(Ph)]⁺, [(napy)Ag₂(Ph)]⁺ and [(napy)CuAg(Ph)]⁺ via extrusion of CO₂ or SO₂ under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu₂(O₂CPh)]⁺, [(napy)Ag₂(O₂CPh)]⁺, [(napy)CuAg(O₂CPh)]⁺ and [(napy)Cu₂(O₂SPh)]⁺, [(napy)Ag₂(O₂SPh)]⁺, [(napy)CuAg(O₂SPh)]⁺. Desulfination was found to be more facile than decarboxylation. Density functional theory calculations reveal that extrusion proceeds via two transition states: TS1 enables isomerization of the O,O-bridged benzoate to its O-bound form; TS2 involves extrusion of CO₂ or SO₂ with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu₂(Ph)]⁺ reacts with water via hydrolysis to give [(napy)Cu₂(OH)]⁺, consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu₂(Ph)(H₂O)]⁺ which then proceeds via TS3 in which the coordinated H₂O is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu₂(OH)(C₆H₆)]⁺, which then loses benzene.

Keywords

Metal carboxylates decarboxylation metal sulfinates desulfination organocopper and organosilver gas phase mass spectrometry density functional theory calculations

Get full access to this article

View all access options for this article.

References

Krause

. Modern organocopper chemistry, Weinheim: John Wiley & Sons, 2002.

Rappoport Z and Marek I (eds). The chemistry of organocopper compounds. Chichester: John Wiley & Sons, 2009.

Alexakis

Bäckvall

Krause

et al.

Enantioselective copper-catalyzed conjugate addition and allylic substitution reactions. Chem Rev 2008; 108: 2796–2823.

Breit

Schmidt

. Directed reactions of organocopper reagents. Chem Rev 2008; 108: 2928–2951.

Weibel

Blanc

Pale

. Ag-mediated reactions: coupling and heterocyclization reactions. Chem Rev 2008; 108: 3149–3173.

Eisch

. Henry Gilman: American pioneer in the rise of organometallic chemistry in modern science and technology. Organometallics 2002; 21: 5439–5463.

Stollenz

Meyer

. Mesitylcopper – a powerful tool in synthetic chemistry. Organometallics 2012; 31: 7708–7727.

Sambiagio

Marsden

Blacker

et al.

Copper catalysed Ullmann type chemistry: from mechanistic aspects to modern development. Chem Soc Rev 2014; 43: 3525–3550.

Gooßen

Thiel

Rodríguez

et al.

Cu-catalyzed protodecarboxylation of aromatic carboxylic acids. Adv Synth Catal 2007; 349: 2241–2246.

10.

Gooßen

Deng

Levy

. Synthesis of biaryls via catalytic decarboxylative coupling. Science 2006; 313: 662–664.

11.

van Koten G and Jastrzebski JTBH. Structural organocopper chemistry. In: Rappoport Z and Marek I (eds) The Chemistry of Organocopper Compounds. Chichester: UK, 2009.

12.

Leoni

Pesquali

Ghilardi

. Isolation and crystal and molecular structure of a rare example of a mononuclear organo-cuprate. J Chem Soc Chem Commun 1983; 5: 240–241.

13.

Bomparola

Davies

Hornauer

et al.

Structural characterization of magnesium organocuprates derived from Grignard reagents: CuI-based inverse crown ethers. Angew Chem Int Ed 2008; 47: 5812–5815.

14.

He X, Olmstead MM and Power PP. Synthesis of [Me₂SCu(C₆H₂-2,4,6-tert-Bu₃)] and [(M_e2S)₂Cu(-C₆H₂-2,4,6-Ph₃)Cu(C₆H₂-2,4,6-Ph₃)]: mononuclear and dinuclear organocopper(I) species of formula [CuR.Solvate]_{1 or 2}.

15.

Ziegler

Levine

Lakshmi

et al.

Aryl group transfer from tetraarylborato anions to an electrophilic dicopper(I) center and mixed-valence μ-aryl dicopper(I,II) complexes. J Am Chem Soc 2016; 138: 6484–6491.

16.

Tate

Jordan

Bacsa

et al.

Stable mono- and dinuclear organosilver complexes. Organometallics 2017; 36: 964–974.

17.

Ruhlandt-Senge

Power

et al.

New copper chemistry. 22. Synthesis and characterization of [Cu₃Ph₂(PMDTA)₂]+: a cationic organocopper(I) species. J Am Chem Soc 1994; 116: 6963–6964.

18.

Meyer

Gambarotta

Floriani

et al.

Polynuclear aryl derivatives of Group 11 metals. Synthesis, solid state-solution structural relationship, and reactivity with phosphines. Organometallics 1989; 8: 1067–1079.

19.

Edwards

Gellert

Marks

et al.

Preparation and structure of the phenylcopper ([Cu₅(C₆H₅)₆]-) anion. J Am Chem Soc 1982; 104: 2072–2073.

20.

van Koten

Noltes

. Synthesis and specific intramolecular C–C coupling reactions of novel hexanuclear copper cluster complexes Ar₄R₂Cu₆. J Chem Soc Chem Commun 1974; 15: 575–576.

21.

Camus

Marsich

Nardin

et al.

The crystal structure ofo-anisylcopper(I): an octameric copper(I) cluster compound. J Organomet Chem 1979; 174: 121–128.

22.

Green

Parkin

. The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds. Chem Commun 2012; 48: 11481–11503.

23.

Gray

Sadighi

. Molecular metal-metal bonds (Liddle ST, ed), Weinheim: Wiley, 2015, pp. 397–428.

24.

O’Hair

RAJ

. The 3D quadrupole ion trap mass spectrometer as a complete chemical laboratory for fundamental gas phase studies of metal mediated chemistry. Chem Commun 2006; 14: 1469–1481.

25.

O’Hair

RAJ

Rijs

. Gas phase studies of the pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions. Acc Chem Res 2015; 48: 329–340.

26.

Khairallah

Waters

O’Hair

RAJ

. C-C bond coupling between the organometallic cations CH₃Ag₂⁺, CH₃Cu₂⁺ and CH₃AgCu⁺ and allyliodide. Dalton Trans 2009; 38: 2832–2836.

27.

Al Sharif

Vikse

Khairallah

et al.

Catalytic decarboxylative coupling of allyl acetate: role of the metal centers in the organometallic cluster cations [CH₃Cu₂]⁺, [CH₃AgCu]⁺ and [CH₃Ag₂]⁺. Organometallics 2013; 32: 5416–5427.

28.

Khairallah

William

Chow

et al.

sp-sp³ coupling reactions of alkynylsilver cations, RC≡CAg₂⁺ (R = Me and Ph) with allyliodide. Dalton Trans 2013; 42: 9462–9467.

29.

Khairallah

Saleeba

Chow

et al.

C-H and C-C bond activation reactions in silver alkynyl cluster cations, RC≡CAg₂⁺. Int J Mass Spectrom 2013; 354: 229–234.

30.

Brunet

Antoine

Broyer

et al.

Structural and photochemical properties of organosilver reactive intermediates MeAg₂⁺ and PhAg₂⁺. J Phys Chem A 2011; 115: 9120–9127.

31.

Vikse

Zavras

Thomas

et al.

Prying open a reactive site for allylic arylation by phosphine-ligated geminally diaurated aryl gold complexes. Organometallics 2015; 34: 3255–3263.

32.

Jin

Ariafard

et al.

Substituent effects in the decarboxylation reactions of coordinated arylcarboxylates in dinuclear copper complexes, [(napy)Cu₂(O₂CC₆H₄X)]⁺. Eur J Mass Spectrom 2017; 23: 351–358.

33.

O’Hair RAJ. Gas phase ligand fragmentation to unmask reactive metallic species. In: Santos LS (ed). Reactive Intermediates: MS Investigations in Solution. Weinheim: Wiley-VCH, 2010, pp. 199–227.

34.

Khairallah

da Silva

O'Hair

RAJ

. Molecular salt effects in the gas phase: tuning the kinetic basicity of [HCCLiCl]^- and [HCCMgCl₂]^- by LiCl and MgCl₂. Angew Chem Int Ed 2014; 53: 10979–10983.

35.

Deacon

. Syntheses of organometallic compounds by thermal decarboxylation. Organomet Chem Rev Sect A 1970; 5: 355–372.

36.

Deacon

Faulks

Pain

. The synthesis of organometallics by decarboxylation reactions. Adv Organomet Chem 1986; 25: 237–276.

37.

Sraj

Khairallah

da Silva

et al.

Who wins: Pesci, Peters, or Deacon? Intrinsic reactivity orders for organocuprate formation via ligand decomposition. Organometallics 2012; 31: 1801–1807.

38.

Rodríguez

Goossen

. Decarboxylative coupling reactions: a modern strategy for C–C-bond formation. Chem Soc Rev 2011; 40: 5030–5048.

39.

Shang

Liu

. Transition metal-catalyzed decarboxylative cross-coupling reactions. Sci China Chem 2011; 54: 1670–1687.

40.

Cornella

Larrosa

. Decarboxylative carbon-carbon bond-forming transformations of (hetero)aromatic carboxylic acids. Synthesis 2012; 44: 653–676.

41.

Dzik

Lange

Gooßen

. Carboxylates as sources of carbon nucleophiles and electrophiles: comparison of decarboxylative and decarbonylative pathways. Chem Sci 2012; 3: 2671–2678.

42.

Gooßen

Rodriguez

Linder

et al.

Decarboxylative coupling reactions. Top Organomet Chem 2013; 44: 121–141.

43.

Aziz

Messaoudi

Alami

et al.

Sulfinate derivatives: dual and versatile partners in organic synthesis. Org Biomol Chem 2014; 12: 9743–9759.

44.

Ortgies

Hassanpour

Chen

et al.

Desulfination as an emerging strategy in palladium-catalyzed C–C coupling reactions. Eur J Org Chem 2016; 3: 408–425.

45.

Colorado

Brodbelt

. An empirical approach to estimation of critical energies by using a quadrupole ion trap. J Am Soc Mass Spectrom 1996; 7: 1116–1125.

46.

Armentrout

. Mass spectrometry – not just a structural tool: the use of guided ion beam tandem mass spectrometry to determine thermochemistry. J Am Soc Mass Spectrom 2002; 13: 419–434.

47.

Zins

Pepe

Schröder

. Energy-dependent dissociation of benzylpyridinium ions in an ion-trap mass spectrometer. J Mass Spectrom 2010; 45: 1253–1260.

48.

Price SWJ, The Decomposition of Metal Alkyls, Aryls, Carbonyls and Nitrosyls, Price. In: Bamford CH, Compton RG, Tippe CFH (eds). Decomposition of Inorganic and Organometallic Compound. Amsterdam: Elsevier, 1972, pp. 197–257.

49.

Whitesides

. Organotransition-metal chemistry, New York: Plenum Press, 1975, pp. 223–229.

50.

Rijs

O’Hair

RAJ

. Unimolecular reactions of organocuprates and organoargenates. Organometallics 2010; 29: 2282–2291.

51.

Khairallah

Thum

Lesage

et al.

Gas-phase formation and fragmentation reactions of the organomagnesates. Organometallics 2013; 32: 2319–2328.

52.

Schmidbaur

Dash

. Organogold chemistry. XIII. 1,8-Naphthyridine complexes of dimethylgold halides and pseudohalides. Simple case of fluxional behavior. J Am Chem Soc 1973; 95: 4855–4860.

53.

Schmidbaur

Schier

. Argentophilic interactions. Angew Chem Int Ed 2015; 54: 746–784.

54.

Zavras

Khairallah

Krstić

et al.

Ligand-induced substrate steering and reshaping of [Ag₂(H)]⁺ scaffold for selective CO₂ extrusion from formic acid. Nature Comm 2016; 7: 11746.

55.

Krstić

Jin

Khairallah

et al.

How to translate the [LCu₂(H)]⁺ catalysed selective decomposition of formic acid into H₂ and CO₂ from the gas-phase into a zeolite. ChemCatChem 2018; 10: 1173–1177.

56.

Kerr JA. Bond dissociation energies in diatomic molecules. In: Haynes WM (ed) CRC handbook of chemistry and physics. 97th ed. Boca Raton: CRC Press/Taylor & Francis, 2017.

57.

Deng

Kebarle

. Bond energies of copper ion−ligand L complexes CuL₂+ determined in the gas phase by ion−ligand exchange equilibria measurements. J Am Chem Soc 1998; 120: 2925–2931.

58.

Deng

Kebarle

. Binding energies of silver ion−ligand, L, complexes AgL₂+ determined from ligand-exchange equilibria in the gas phase. J Phys Chem A 1998; 102: 571–579.

59.

Rodgers

Armentrout

. Cationic noncovalent interactions: energetics and periodic trends. Chem Rev 2016; 116: 5642–5687.

60.

Sanchez

Cornella

et al.

Silver-catalyzed protodecarboxylation of heteroaromatic carboxylic acids. Org Lett 2009; 11: 5710–5713.

61.

Gooßen

Linder

Rodríguez

et al.

Silver-catalysed protodecarboxylation of carboxylic acids. Chem Commun 2009; 46: 7173–7175.

62.

Brauman

. Some historical background on the double–well potential model. J Mass Spectrom 1995; 30: 1649–1651.

63.

Lotz

Camasso

Canty

et al.

Role of silver salts in palladium-catalyzed arene and heteroarene C–H functionalization reactions. Organometallics 2017; 36: 165–171.

64.

Niedner-Schatteburg

Cooperative effects in clusters and oligonuclear complexes of transition metals in isolation. In: Dehnen

(eds). Clusters – contemporary insight in structure and bonding, Cham: Springer International Publishing, 2017, pp. 1–40.

65.

Pérez-Temprano

Casares

Espinet

. Bimetallic catalysis using transition and group 11 metals: an emerging tool for C-C coupling and other reactions. Chem Eur J 2012; 18: 1864–1884.

66.

Mankad

. Selectivity effects in bimetallic catalysis. Chem Eur J 2016; 22: 5822–5829.

67.

Donald

McKenzie

O'Hair

RAJ

. C–H bond activation of methanol and ethanol by a high-spin Fe^IVO biomimetic complex. Angew Chem Int Ed 2011; 50: 8379–8383.

68.

Donald

Khairallah

O'Hair

RAJ

. The effective temperature of ions stored in a linear quadrupole ion trap mass spectrometer. J Am Soc Mass Spectrom 2013; 24: 811–815.

69.

Bowers

. Ion-polar molecule collisions. Effect of size on ion-polar molecule rate constants. Paramterization of the average-dipole-orientation theory. Int J Mass Spectrom Ion Phys 1973; 12: 347–356.

70.

Lim

. COLRATE. QCPE 643: calculation of gas-kinetic collision rate coefficients. QCPE Bull 1994; 14: 3.

71.

Frisch

et al.

Gaussian 09, Revision D.01, Wallingford: Gaussian, Inc, 2009.

72.

Zhao

Truhlar

. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 2008; 120: 215–241.

73.

Dolg

Wedig

Stoll

et al.

Energy-adjusted ab initio pseudopotentials for the first row transition elements. J Chem Phys 1987; 86: 866–872.

74.

Petersson

Bennett

Tensfeldt

et al.

A complete basis set model chemistry. I. The total energies of closed-shell atoms and hydrides of the first-row elements. J Chem Phys 1988; 89: 2193–2218.

75.

Petersson

Al-Laham

. A complete basis set model chemistry. II. Open-shell systems and the total energies of the first-row atoms. J Chem Phys 1991; 94: 6081–6090.

76.

Peng

Schlegel

. Combining synchronous transit and quasi-newton methods to find transition states. Isr J Chem 1993; 33: 449–454.

77.

Peng

Ayala

Schlegel

et al.

Using redundant internal coordinates to optimize equilibrium geometries and transition states. J Comput Chem 1996; 17: 49–56.

78.

Fukui

. Formulation of the reaction coordinate. J Phys Chem 1970; 74: 4161–4163.

79.

Fukui

. The path of chemical reactions – the IRC approach. Acc Chem Res 1981; 14: 363–368.

Supplementary Material

Please find the following supplemental material available below.

For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.

For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.

0.00 MB

2.15 MB

Formation and reactions of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu 2 (Ph)] +,[(napy)Ag 2 (Ph)] + and [(napy)CuAg(Ph)] +

Abstract

Keywords

Get full access to this article

References

Supplementary Material