Isotope labeling and infrared multiple-photon photodissociation investigation of product ions generated by dissociation of [ZnNO 3 (CH 3 OH) 2 ] + : Conversion of methanol to formaldehyde

Abstract

Electrospray ionization was used to generate species such as [ZnNO₃(CH₃OH)₂]⁺ from Zn(NO₃)₂•XH₂O dissolved in a mixture of CH₃OH and H₂O. Collision-induced dissociation of [ZnNO₃(CH₃OH)₂]⁺ causes elimination of CH₃OH to form [ZnNO₃(CH₃OH)]⁺. Subsequent collision-induced dissociation of [ZnNO₃(CH₃OH)]⁺ causes elimination of 47 mass units (u), consistent with ejection of HNO₂. The neutral loss shifts to 48 u for collision-induced dissociation of [ZnNO₃(CD₃OH)]⁺, demonstrating the ejection of HNO₂ involves intra-complex transfer of H from the methyl group methanol ligand. Subsequent collision-induced dissociation causes the elimination of 30 u (32 u for the complex with CD₃OH), suggesting the elimination of formaldehyde (CH₂ = O). The product ion is [ZnOH]⁺. Collision-induced dissociation of a precursor complex created using CH₃-¹⁸OH shows the isotope label is retained in CH₂ = O. Density functional theory calculations suggested that the “rearranged” product, ZnOH with bound HNO₂ and formaldehyde is significantly lower in energy than ZnNO₃ with bound methanol. We therefore used infrared multiple-photon photodissociation spectroscopy to determine the structures of both [ZnNO₃(CH₃OH)₂]⁺ and [ZnNO₃(CH₃OH)]⁺. The infrared spectra clearly show that both ions contain intact nitrate and methanol ligands, which suggests that rearrangement occurs during collision-induced dissociation of [ZnNO₃(CH₃OH)]⁺. Based on the density functional theory calculations, we propose that transfer of H, from the methyl group of the CH₃OH ligand to nitrate, occurs in concert with the formation of a Zn–C bond. After dissociation to release HNO₂, the product rearranges with the insertion of the remaining O atom into the Zn–C bond. Subsequent C–O bond cleavage, with H transfer, produces an ion–molecule complex composed of [ZnOH]⁺ and O = CH₂.

Keywords

Metal-mediated reactions tandem mass spectrometry infrared multiple-photon photodissociation ion spectroscopy ion structure

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References

Vachet

Callahan

. Quadrupole ion trap studies of the structure and reactivity of transition metal ion pair complexes. J Mass Spectrom 2000; 35: 311–320.

Combariza

Vachet

. Gas-phase ion-molecule reactions of transition metal complexes: the effect of different coordination spheres on complex reactivity. J Am Soc Mass Spectrom 2002; 13: 813–825.

Combariza

Fermann

Vachet

. Are gas-phase reactions of five-coordinate divalent metal ion complexes affected by coordination geometry?. Inorg Chem 2004; 43: 2745–2753.

Eller

Schwarz

. Organometallic chemistry in the gas phase. Chem Rev 1991; 91: 1121–1177.

Böhme

Schwarz

. Gas-phase catalysis by atomic and cluster metal ions: the ultimate single-site catalysts. Angew Chem Int Ed 2005; 44: 2336–2354.

O'Hair

RAJ

. Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters. Pure Appl Chem 2015; 87: 391–404.

O'Hair

RAJ

. Mass spectrometry based studies of gas phase metal catalyzed reactions. Int J Mass Spectrom 2015; 377: 121–129.

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.

Jirasko

Holcapek

. Structural analysis of organometallic compounds with soft ionization mass spectrometry. Mass Spectrom Rev 2011; 30: 1013–1036.

10.

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, pp. 1469–1481.

11.

Armentrout

. The power of accurate energetics (or thermochemistry: what is it good for?). J Am Soc Mass Spectrom 2013; 24: 173–185.

12.

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.

13.

Brodbelt

. Analytical applications of ion-molecule reactions. Mass Spectrom Rev 1997; 16: 91–110.

14.

Osburn

Ryzhov

. Ion−molecule reactions: analytical and structural tool. Anal Chem 2013; 85: 769−778.

15.

Dunbar

. Photodissociation of trapped ions. Int J Mass Spectrom 2000; 200: 571.

16.

Duncan

. Frontiers in the spectroscopy of mass-selected molecular ions. Int J Mass Spectrom 2000; 200: 545.

17.

Polfer

Oomens

. Reaction products in mass spectrometry elucidated with infrared spectroscopy. Phys Chem Chem Phys 2007; 9: 3804.

18.

Polfer

. Infrared multiple photon dissociation spectroscopy of trapped ions. Chem Soc Rev 2011; 40: 2211–2221.

19.

MacAleese

Maitre

. Infrared spectroscopy of organometallic ions in the gas phase: from model to real world complexes. Mass Spectrom Rev 2007; 26: 583.

20.

Jasikova

Roithova

. Infrared multiphoton dissociation Spectroscopy with free-electron lasers: on the road from small molecules to biomolecules. Chem Eur J 2018; 24: 3374–3390.

21.

Roithova

. Characterization of reaction intermediates by ion spectroscopy. Chem Soc Rev 2012; 41: 547–559.

22.

Vallee BL and Auld DS. Active zinc binding sites of zinc metalloenzymes. In: Birkedal-Hansen H (ed.) Matrix metalloproteinases inhibitors, Proceedings of matrix metalloproteinase conference. Stuttgart: Fisher, 1992, pp. 5–19.

23.

Parkin

. Synthetic analogues relevant to the structure and function of zinc enzymes. Chem Rev 2004; 104: 699–767.

24.

Martens

Berden

Gebhardt

et al.

Infrared ion spectroscopy in a modified quadrupole ion trap mass spectrometer at the FELIX free electron laser laboratory. Rev Sci Instrum 2016; 87: 103108-1-103108–8.

25.

Frisch

Trucks

Schlegel

et al.

Gaussian 09, Revision A.02, Wallingford, CT: Gaussian, Inc., 2016.

26.

Peng

Schlegel

. Combining synchronous transit and quasi-Newton methods for finding transition states. Israel J Chem 1993; 33: 449–454.

27.

Vachet

Hartmann

JAR

Callahan

. Ion-molecule reactions in a quadrupole ion trap as a probe of the gas-phase structure of metal complexes. J Mass Spectrom 1998; 33: 1209–1225.

28.

Perera

Ince

Talaty

et al.

Gas phase attachment of water and methanol to Ag⁺ complexes with α-amino acids in an ion trap mass spectrometer. Rapid Commun Mass Spectrom 2001; 15: 615–622.

29.

Hanna

Silva

Morrison

et al.

Gas-phase hydration and alcohol addition reactions of complexes composed of Ag⁺ and a single alcohol molecule. J Phys Chem A 2003; 107: 5528–5537.

30.

Harrington

Cao

Scott

et al.

Gas-phase hydration of U(IV), U(V) and U(VI) oxo cations. J Phys Chem A 2003; 107: 8530–8538.

31.

Van Stipdonk

Gresham

Groenewold

et al.

Elucidation of the collision-induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation. J Am Soc Mass Spectrom 2003; 14: 1205–1214.

32.

Leavitt

Oomens

Dain

et al.

IRMPD spectroscopy of anionic group II metal nitrate clusters. J Am Soc Mass Spectrom 2009; 20: 722–782.

33.

Oomens

Myers

Dain

et al.

Infrared multiple-photon photodissociation of gas-phase group II metal-nitrate anions. Int J Mass Spectrom 2008; 273: 24–30.

34.

Groenewold

Oomens

de Jong

et al.

Vibrational spectroscopy of anionic nitrate complexes of

{UO}_{2}^{2 +}

and Eu³⁺ isolated in the gas phase. Phys Chem Chem Phys 2008; 10: 1192–1202.

35.

Krasovsky

Malakhov

Gavryshin

et al.

Efficient synthesis of functionalized organozinc compounds by the direct insertion of zinc into organic iodides and bromides. Angew Chem Int Ed 2006; 45: 6040–6044.

36.

Kochel

Singer

. Preparation and reaction of polyfunctional organozinc reagents in organic synthesis. Chem Rev 1993; 93: 2117–2186.

37.

Dreiocker

Oomens

Meijer

AJHM

et al.

Structure elucidation of dimethylformamide-solvated alkylzinc cations in the gas phase. J Org Chem 2010; 73: 1203–1213.

38.

Massah

Dreiocker

Jackson

RFW

et al.

Gas-phase study of new organozinc reagents by IRMPD-spectroscopy, computational modeling and tandem-MS. Phys Chem Chem Phys 2011; 13: 13255–13267.

39.

Casey

Andrews

McAlister

. Disproportionation of a neutral metal-formyl complex and synthesis of a stable hydroxymethyl-metal compound. J Am Chem Soc 1979; 101: 3371–3373.

40.

von Ragué Schleyer

Clark

Kos

et al.

Structures and stabilities of α-hetero-substituted organolithium and organosodium compounds. Energetic unimportance of second-row d-orbital effects. J Am Chem Soc 1884; 22: 6467–6475.

41.

Krief

. Synthetic methods using α-heterosubstituted organometallics. Tetrahedron 1980; 36: 2531–2640.

42.

Yasuda

Azuma

Tsuruwa

et al.

Highly stereoselective synthesis of vicinal diols by stannous chloride-mediated addition of hydroxylic stannanes to aldehydes. Tetrahedron Lett 2009; 50: 3209–3212.

43.

Yasuda

Tsuruwa

Azuma

et al.

Stereoselective synthesis of vicinal diols by the stannous chloride-mediated reaction of unprotected hydroxyallylic stannane with carbonyl compounds. Tetrahedron 2009; 65: 9569–9574.

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