The preparation and crystal structures of some tricarbonylmanganese(I) octahedral complexes containing the 1,1-dimethylamino-2,2-diphenylphosphinoethane ligand

Bauer, Jeanette A. Krause; Becker, Thomas; Orchin, Milton

doi:10.1007/s10870-004-7717-1

Cited by 18 publications

(6 citation statements)

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“…Crystals of 1 ·[Mn(CO) 3 (H 2 O)]Br were soaked in a methanol solution of sodium azide (NaN 3 ) for 3 days to yield 1 ·[Mn(CO) 3 N 3 ]. The IR spectrum of 1 ·[Mn(CO) 3 N 3 ] revealed a strong IR stretch at 2070 cm –1 that is typical of a metal-coordinated azide; ,− furthermore, the expected ν(CO) bands were observed at 2025, 1952, and 1903 cm –1 . The elemental composition of 1 ·[Mn(CO) 3 N 3 ] was assessed by EDX analysis to provide insight into the extent of Br – substitution.…”

Section: Resultsmentioning

confidence: 99%

“…N(1)-bound octahedral triazolate complexes, such as 1 ·[Mn(CO) 3 (DMT)] and 1 ·[Mn(CO) 3 (ET)], are rare, ,− because steric effects in octahedral complexes usually favor the rearrangement of the complex to form the N(2)-bound isomer. , It is evident from the crystal structures that close contacts between the coordinated triazolate and adjacent features of the MOF pore would be substantially increased if the triazolate were to bind via the N(2) nitrogen. To confirm that the MOF environment, rather than the primary coordination environment, is responsible for this behavior, we synthesized the molecular counterpart, [Mn(bis(3,5-dimethyl-pyrazolyl)methane)(CO) 3 (dimethyl 4,5-carboxy-1,2,3-triazolate)] ([Mn(bpm)(CO) 3 (DMT)], where bpm = bis(3,5-dimethyl-pyrazolyl)methane).…”

Section: Resultsmentioning

confidence: 99%

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Protecting-Group-Free Site-Selective Reactions in a Metal–Organic Framework Reaction Vessel

et al. 2018

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Site-selective organic transformations are commonly required in the synthesis of complex molecules. By employing a bespoke metal-organic framework (MOF, 1·[Mn(CO)N]), in which coordinated azide anions are precisely positioned within 1D channels, we present a strategy for the site-selective transformation of dialkynes into alkyne-functionalized triazoles. As an illustration of this approach, 1,7-octadiyne-3,6-dione stoichiometrically furnishes the mono-"click" product N-methyl-4-hex-5'-ynl-1',4'-dione-1,2,3-triazole with only trace bis-triazole side-product. Stepwise insights into conversions of the MOF reaction vessel were obtained by X-ray crystallography, demonstrating that the reactive sites are "isolated" from one another. Single-crystal to single-crystal transformations of the Mn(I)-metalated material 1·[Mn(CO)(HO)]Br to the corresponding azide species 1·[Mn(CO)N] with sodium azide, followed by a series of [3+2] azide-alkyne cycloaddition reactions, are reported. The final liberation of the "click" products from the porous material is achieved by N-alkylation with MeBr, which regenerates starting MOF 1·[Mn(CO)(HO)]Br and releases the organic products, as characterized by NMR spectroscopy and mass spectrometry. Once the dialkyne length exceeds the azide separation, site selectivity is lost, confirming the critical importance of isolated azide moieties for this strategy. We postulate that carefully designed MOFs can act as physical protecting groups to facilitate other site-selective and chemoselective transformations.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Protecting-Group-Free Site-Selective Reactions in a Metal–Organic Framework Reaction Vessel

et al. 2018

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“…A survey of the literature reveals that reactions between metalazide complexes and electron deficient alkynes have been observed for a few neutral Co 11 and Ni 12 coordination compounds, as well as several organometallic complexes of Ta, 13 Ru, [14][15][16] Fe, 15 Mn, 17 Au, 18 Os, 19 and Mo 20 (Scheme 3). In addition, a "fully" inorganic click reaction between a metalazide and a metal-acetylide has been reported recently.…”

Section: Introductionmentioning

confidence: 99%

Cycloaddition reactivity studies of first-row transition metal–azide complexes and alkynes: an inorganic click reaction for metalloenzyme inhibitor synthesis

2012

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The studies described herein focus on the 1,3-dipolar cycloaddition reaction between first-row transition metal-azide complexes and alkyne reagents, i.e. an inorganic variant of the extensively used "click reaction". The reaction between the azide complexes of biologically-relevant metals (e.g., Fe, Co and Ni) found in metalloenzyme active sites and alkyne reagents has been investigated as a proof-of-principle for a novel method of developing metalloenzyme triazole-based inhibitors. Six Fe, Co and Ni mono-azide complexes employing salen- and cyclam-type ligands have been synthesized and characterized. The scope of the targeted inorganic azide-alkyne click reaction was investigated using the electron-deficient alkyne dimethyl acetylenedicarboxylate. Of the six metal-azide complexes tested, the Co and Ni complexes of the 1,4,8,11-tetrametyl-1,4,8,11-tetraazacyclotetradecane (Me(4)cyclam) ligand showed a successful cycloaddition reaction and formation of the corresponding metal-triazolate products, which were crystallographically characterized. Moreover, use of less electron deficient alkynes resulted in a loss of cycloaddition reactivity. Analysis of the structural parameters of the investigated metal-azide complexes suggests that a more symmetric structure and charge distribution within the azide moiety is needed for the formation of a metal-triazolate product. Overall, these results suggest that a successful cycloaddition reaction between a metal-azide complex and an alkyne substrate is dependent both on the ligand and metal oxidation state, that determine the electronic properties of the bound azide, as well as the electron deficient nature of the alkyne employed.

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“… 3 Metal azido complexes have a rich cycloaddition chemistry. 4 – 6 A range of d-block azido complexes, including those of Mn( i ), 7 , 8 Fe( iii ), 9 Pd( ii ), 10 Pt( ii ), 10 – 15 Rh( iii ) 16 and Au( i ), 17 have been reported to undergo copper-free 1,3-dipolar cycloaddition or “click” reactions with carbon–carbon and carbon-heteroatom functional groups such as alkynes, isocyanides, isonitriles, nitriles, carbon disulphides and isothiocyanates. Electron-deficient alkynes such as dimethyl acetylenedicarboxylate (DMAD) and diethyl acetylenedicarboxylate (DEACD) are relatively reactive: Mo( ii ), 16 , 18 Co( iii ), 19 Fe( iii ) 19 , 20 Ru( ii ), 20 – 25 Pd( ii ) 26 – 28 and Ta 29 azido complexes all react with DMAD.…”

Section: Introductionmentioning

confidence: 99%

Platinum(iv) azido complexes undergo copper-free click reactions with alkynes

et al. 2018

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The preparation and crystal structures of some tricarbonylmanganese(I) octahedral complexes containing the 1,1-dimethylamino-2,2-diphenylphosphinoethane ligand

Cited by 18 publications

References 18 publications

Protecting-Group-Free Site-Selective Reactions in a Metal–Organic Framework Reaction Vessel

Protecting-Group-Free Site-Selective Reactions in a Metal–Organic Framework Reaction Vessel

Cycloaddition reactivity studies of first-row transition metal–azide complexes and alkynes: an inorganic click reaction for metalloenzyme inhibitor synthesis

Platinum(iv) azido complexes undergo copper-free click reactions with alkynes

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