Incorporation of alkyne and vinylidene ligands into tetrazolate groups at a sulfur-rich dimolybdenum site using sodium azide

Schollhammer, Philippe; Cabon, Nolwenn; Kervella, Anne-Cécile; Pétillon, François Y.; Rumin, René; Talarmin, Jean; Muir, Kenneth W.

doi:10.1016/s0020-1693(02)01556-6

Cited by 10 publications

(12 citation statements)

References 53 publications

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“…According to X-ray diffraction data, complex 107 (R = Ph) contains two cluster molybdenum atoms [the Mo7Mo bond length is 2.7913(6) # A], one being bonded to the heterocycle N(1) atom, while the other, to the a-carbon atom; substantial electron delocalisation occurs in the Mo7C7C(5) fragment. 143 …”

Section: Synthesis Of Metal Derivatives Of Tetrazoles By Heterocyclismentioning

confidence: 99%

Metal derivatives of tetrazoles

Гапоник¹,

2006

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Published data on the synthesis, structure, properties Published data on the synthesis, structure, properties and applications of metal derivatives of tetrazoles are generalised and applications of metal derivatives of tetrazoles are generalised and described systematically. Compounds based on the anionic and described systematically. Compounds based on the anionic and neutral tetrazole forms, and neutral tetrazole forms, C C-and -and N N-mono-and -mono-and C C, ,N N-disubsti--disubstituted tetrazoles are considered. The bibliography includes 464 tuted tetrazoles are considered. The bibliography includes 464 references references. . ReceivedDepending on the reaction conditions, meta-and para-5,5 Hphenyleneditetrazoles 25 react with Cd, Zn and Mn(II) salts to give essentially different, as regards both composition and structure, complexes 26, 27, 44 28, 45 29. 46 The structures of compounds 26 ± 29 were determined by X-ray diffraction. Compounds 26 ± 28 in which the doubly charged anions derived from tetrazole 25 function as bridges are two-and three-dimensional coordination polymers. Conversely, compound 29 is a mononuclear aqua complex containing no metal ± tetrazole coordination bond. In the structure of complex 28, one-dimensional channels were found which occupy up to 35% of the void volume and encapsulate tetrameric cyclic water clusters and DMF molecules. On heating to 150 8C, water and DMF are removed from the channels, which accounts for the interest of researchers in this type of compound for the preparation of inclusion compounds and sorbents. A coordination polymer with a composition similar to complex K + 7

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Section: Synthesis Of Metal Derivatives Of Tetrazoles By Heterocyclismentioning

confidence: 99%

Metal derivatives of tetrazoles

Гапоник¹,

2006

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“…We have also described the activation of other small, unsaturated molecules, such as terminal alkynes (HC⋮CR) (Scheme ), isocyanides (RN⋮C), and nitriles (RC⋮N), by the {Mo III 2 Cp 2 } system . The conversion of the alkyne adduct [Mo 2 Cp 2 (μ-SMe) 3 (HC⋮CR)](BF 4 ) ( B ; Cp = η 5 -C 5 H 5 ) into the readily accessible vinylidene derivative [Mo 2 Cp 2 (μ-SMe) 3 (μ-η 1 :η 2 -CCHR)](BF 4 ) ( D ) (Scheme ) was the starting point for new studies 6 focused on the transformations of hydrocarbyl groups at this sulfur-rich site.…”

Section: Introductionmentioning

confidence: 99%

Transformations and Agostic Interactions of Hydrocarbyl Ligands Bonded to the Sulfur-Rich Dimolybdenum Site {Mo₂Cp₂(μ-SMe)₃}: Chemical and Electrochemical Formation of μ-Alkyl and μ-Vinyl Compounds from a μ-Alkylidene Derivative

et al. 2005

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A series of chemical and electrochemical transformations of systems in which a {Mo2Cp2(μ-SMe)3} core is bridged by a μ-C2H n R ligand (n = 0−4) are described in this paper. The reaction of the alkylidene complex [Mo2Cp2(μ-SMe)3(μ-η1:η2-CHCH2Tol)](BF4) (1) with LiBun at 0 °C produces the μ-σ,π-vinyl complex [Mo2Cp2(μ-SMe)3((μ-η1:η2-CHCHTol] (2) in good yield. The molecular structure of 2 has been confirmed by X-ray analysis. Upon treatment with NaBH4 1 is readily converted into the semibridging alkyl species [Mo2Cp2(μ-SMe)3(μ-CH2CH2Tol)] (3), which is also formed by electrochemical reduction of 1 in acidic medium. NMR and X-ray diffraction studies of 3 are consistent with, but do not definitively establish, the presence of a η1 α-agostic interaction. Density functional theory has been used to confirm the presence of agostic interactions in both 1 and 3 and also to explore the exchange pathways for these hydrocarbyl dimolybdenum systems. Electrochemical transformation of the μ-alkylidene complex 1 gives 3 as the major product when acid is present and a mixture of 2 and 3 when acid is absent, production of 2 being favored by low initial concentrations of 1. Theoretical, spectroscopic, and diffraction data are used to explain the formation and structures of closely related [Mo2Cp2(μ-SMe)3(μ-C2H n R] z + complexes (n = 0−4 and z = 0, 1), including 1−3.

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“…Scheme 4, section 1.2.). [360] A close parallel to this work may be seen in the synthesis of the tetrazolate complex 49 from a rutheniumbound cyanocyclopropenyl ligand 48 which also passes through vinylidene and N-coordinated nitrile intermediates ( Table 3). The involvement of the latter has been proven by its isolation and X-ray structure determination.…”

Section: Reviewmentioning

confidence: 72%

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

Fehlhammer

Beck

2015

Zeitschrift anorg allge chemie

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Abstract. In whatever state of bonding -whether covalent to an organic residue or a heteroatom, or polar to ionic in contact with a metal -the azide moiety N 3 is characterized by its high potential of reactivity which essentially manifests itself in two basic processes: the elimination of dinitrogen and the entry into 1,3-dipolar cycloadditions with suitable dipolarophiles, the latter of which clearly predominates the chemistry of azide, also that of its metal compounds. In a preceding review entitled "Part I -Metal Azides: Overview, General Trends and Recent Developments" which was meant to lay the foundations for the present paper, these and other reactions have already been touched upon. The present review -Part II -now focusses in great detail on the formation of five-membered heterocyclestetrazol(at)es, triazol(at)es, triazolin(at)es, thiatriazol(at)es, etc. as well as various consecutive products -from azide and nitriles, isocyanides, alkynes, alkenes and heteroallenes (CS 2 , RN=C=S) in the ligand sphere of the metal. Generally, these [3+2]-cycloadditions are found to CONTENTS

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Incorporation of alkyne and vinylidene ligands into tetrazolate groups at a sulfur-rich dimolybdenum site using sodium azide

Cited by 10 publications

References 53 publications

Metal derivatives of tetrazoles

Metal derivatives of tetrazoles

Transformations and Agostic Interactions of Hydrocarbyl Ligands Bonded to the Sulfur-Rich Dimolybdenum Site {Mo₂Cp₂(μ-SMe)₃}: Chemical and Electrochemical Formation of μ-Alkyl and μ-Vinyl Compounds from a μ-Alkylidene Derivative

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

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Incorporation of alkyne and vinylidene ligands into tetrazolate groups at a sulfur-rich dimolybdenum site using sodium azide

Cited by 10 publications

References 53 publications

Metal derivatives of tetrazoles

Metal derivatives of tetrazoles

Transformations and Agostic Interactions of Hydrocarbyl Ligands Bonded to the Sulfur-Rich Dimolybdenum Site {Mo2Cp2(μ-SMe)3}: Chemical and Electrochemical Formation of μ-Alkyl and μ-Vinyl Compounds from a μ-Alkylidene Derivative

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

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Transformations and Agostic Interactions of Hydrocarbyl Ligands Bonded to the Sulfur-Rich Dimolybdenum Site {Mo₂Cp₂(μ-SMe)₃}: Chemical and Electrochemical Formation of μ-Alkyl and μ-Vinyl Compounds from a μ-Alkylidene Derivative

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems