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

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

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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.

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