Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates

Luo, Ming; Long, L. H.; Zhang, Hong; Yang, Yuhui; Hua, Yuhui; Liu, Gang; Lin, Zhenyang; Xia, Haiping

doi:10.1021/jacs.6b13275

Cited by 61 publications

(27 citation statements)

References 57 publications

(21 reference statements)

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“…All the salient features of 1 compare well with those of previously reported aromatic osmapentalynes 39 . Osmapentalynes and related osmium chelates with multidentate carbon ligands have attracted considerable attention as novel aromatic molecules with unique properties, especially in the area of photophysics 39 – 43 , 48 . However, previous methods reported for the synthesis of these chelates with multidentate carbon ligands require the use of an unstable osmacycle precursor via standard Schlenk techniques 39 – 43 , 48 .…”

Section: Resultsmentioning

confidence: 99%

“…In recent years, our research has focused on the construction of as many metal–carbon σ bonds as possible between a carbon ligand and a metal center, achieving a series of conjugated carbon-ligated multidentate chelates, termed carbolong complexes, with novel structures and unique properties 39 – 43 . All of these complexes contain three or more metal–carbon σ bonds; however, these metal–carbon σ bonds could only be constructed step by step.…”

Section: Introductionmentioning

confidence: 99%

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Multiyne chains chelating osmium via three metal-carbon σ bonds

et al. 2017

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Although the formation of metal–carbon σ bonds is a fundamental principle in organometallic chemistry, the direct bonding of one organic molecule with one metal center to generate more than two metal–carbon σ bonds remains a challenge. Herein, we report an aromaticity-driven method whereby multiyne chains are used to construct three metal–carbon σ bonds in a one-pot reaction under mild conditions. In this method, multiyne chains act as ligand precursors capable of chelating an osmium center to yield planar metallapolycycles, which exhibit aromaticity and good stability. The direct assembly of various multiyne chains with commercially available metal complexes or even simple metal salts provides a convenient and efficient strategy for constructing all carbon-ligated chelates on the gram scale.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Multiyne chains chelating osmium via three metal-carbon σ bonds

et al. 2017

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“…For example, with sodium methanethiolate (under aC Oa tmosphere) 59 is obtained( Scheme 20). [19] Like metallapentalynes,t he metallapentalene derivatives have an eight-p-electron count and exhibit Mçbius aromaticity.F urther examples of the ambiphilic nature of the carbyne carbon in these metallapentalynes are given by the electrophilic addition of halogens [209] and the nucleophilic addition of isocyanides, [210] phenol [211] or anilines. [211,212] Unexpectedly,t reatment Concept of 57 with HBF 4 causes at automeric shift of the triple bond to give the closely related osmapentalyne 58,t hrough an isolable 16 e À metallapentalene intermediate.…”

Section: Metalla-analogues Of Classical Antiaromatic Compoundsmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

146

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Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused-ring metallabenzenes, heterometallabenzenes, π-coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla-analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla-analogues of the anti-aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro-metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications.

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“…[1] Heterometallacycles as well as all-carbon metallacyclesw ith exocyclic heteroatoms can be accessed by using substrates and/orl igands such as CO 2 , [2] phospha-alkynes, [3] nitriles, [4] and isonitriles. [5] The versatility of isonitriles as ligandsw as thoroughly reviewed only recently. [6] We have demonstrated that isonitriles are versatile ligands fort he realisation of av ariety of coordination as wella sC ÀCa nd CÀNc oupling products at zirconocene and hafnocene fragments.…”

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Redox‐Disproportionation of a Decamethyltitanocene(III) Isonitrile Alkynyl Complex

Reiß

Altenburger

Hollmann

et al. 2017

Chemistry A European J

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DedicatedtoKarel Mach on the occasiono fhis 80 th birthday.Abstract: Am ixed decamethyltitanocene(III) isonitrile alkynyl complex (7)w as synthesized by the sequential introduction of the isonitrile and alkynyl ligands. Direct synthesis results in the formationo ft he diamagneticd ecamethyltitanocene bis(isonitrile) (2)a nd bis(alkynyl) (3) complexes. Compound 7 undergoes disproportionation at room temperature to give 2 and 3.A ll complexes were fully characterizedb yI R, NMR, and EPR spectroscopy,a nd mass spectrometry.M olecular structures for complexes 2 and 7 are reported. The stability and reactivity of these complexesa re rationalized by DFT computations.The formation of metallacycles by intermolecular coupling of unsaturated substrates or intramolecular coupling of ligandsi s known in organometallic chemistry andh as allowed for the synthesis of highly straineda nd exotic structures.[1] Heterometallacycles as well as all-carbon metallacyclesw ith exocyclic heteroatoms can be accessed by using substrates and/orl igands such as CO 2 , [2] phospha-alkynes, [3] nitriles, [4] and isonitriles.[5] The versatility of isonitriles as ligandsw as thoroughly reviewed only recently.[6] We have demonstrated that isonitriles are versatile ligands fort he realisation of av ariety of coordination as wella sC ÀCa nd CÀNc oupling products at zirconocene and hafnocene fragments.[5a] Depending on the ratio of metallocene precursor and isonitrile, complexes showing different unusuals tructural motifs were identified and interconversion reactions were investigated. In general, exocyclic N-substitution was predicted to be favourable for the realisation of small, highly strainedm etallacycles. [7] We thus considered the combination of an isonitrile fragment with an alkyne or alkynyl complex as ap romising approach to access these.I nt his contribution, we reportt he synthesis and characterization of am ixed decamethyltitanocene isonitrile alkynyl complex. In solution this complex shows an equilibrium with the corresponding bis(isonitrile) and bis(alkynyl)complexes by disproportionation.These complexes can be regarded as potential precursorsf or the design of small, highly strained and exotic four-membered (hetero)metallacycles.In order to evaluatet he possibility of ad irect synthesis of am ixed titanocene(III) isonitrile alkynyl compound, we performed ar eaction of Cp* 2 TiCl (1)w ith 2,6-dimethylphenylisonitrile (XyNC) and lithium alkynyl compound LiC 2 SiMe 3 (Liac) (Scheme 1). The latter wasp repared by lithiation of trimethylsilylacetylene, isolated as ac olourless solid in good yield and unequivocally identified based on its NMR ( 29 Si: d = À30.3 ppm) and Raman data(1985 cm À1 ).[8]After workupi nn-hexanew eo bserved precipitation of am ixture of two different crystalline compounds,w hich could not be isolated by fractionalcrystallisation but were successfully separated by crystal picking. The 1 HNMR spectrum of this mixture clearly reveals the presence of two different diamagnetic decamethyltitanocene complexes ( C 5 Me ...

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Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates

Cited by 61 publications

References 57 publications

Multiyne chains chelating osmium via three metal-carbon σ bonds

Multiyne chains chelating osmium via three metal-carbon σ bonds

Recent Advances in Metallaaromatic Chemistry

Redox‐Disproportionation of a Decamethyltitanocene(III) Isonitrile Alkynyl Complex

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