cMOF Evidence Base

Synthesis evidence

2-Cyano-2-isonitrosoacetamide and its Ag(I) complexes. Silver(I) cyanoximate as a non-electric gas sensor

Gerasimchuk N., Esaulenko A.N., Dalley K.N. et al. · Dalton Transactions · 2010 · 749-764

7 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Partial recipeSource: Main

Route 1: Other

p005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1

Metal precursorsAgNO3
Linker precursorscesium cyanoximate salt 5
Solventsaqueous solutions; water and methanol wash
Temperatureambient
Work-upVigorous stirring of AgNO3 and 5 in a 1:1 ratio; bright-yellow thick lumpy precipitate filtered, washed with water then methanol, and dried in vacuum desiccator over P2O5.
Activationvacuum desiccator over P2O5
Scalability contextAuthors state complex 6 is easy to make from commercially available precursors, but no scale-up route is reported.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceAgNO31 : 1 ratio with 5p005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1
Linkercompound 51 : 1 ratio with AgNO3p005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1
Solventwateraqueous solution and washp005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1
Solventmethanolwashp005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1
AdditiveP2O5desiccator drying agentp005 / article p.753 · Synthesis of compounds - Silver(I) complexes 6-9 · Scheme 1
Partial recipeSource: Main

Route 2: Other

p006 / article p.754 · Synthesis of compounds

Metal precursorspre-synthesised complex 6, 0.250 g (1.1 mM reported)
Linker precursors2-picoline as N-donor ligand and solvent
Solventshot 2-picoline, 3 mL
AdditivesNaOH pellets in storage desiccator
Temperaturehot 2-picoline; decomposition to 6 on slow heating to approximately 85 C
Work-upDissolve 6 in hot 2-picoline in a test tube; dark-yellow prisms on vessel walls filtered and stored tightly closed over NaOH pellets.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecomplex 60.250 g (1.1 mM reported)p006 / article p.754 · Synthesis of compounds
Solvent2-picoline3 mL · hotp006 / article p.754 · Synthesis of compounds
Partial recipeSource: Main

Route 3: Other

p006 / article p.754 · Synthesis of compounds

Metal precursorspre-synthesised complex 6
Linker precursorsammonia ligands from aqueous 30% ammonia
Solventsaqueous 30% ammonia; ethanol vapour
Atmosphereethanol vapour diffusion
Temperatureambient
Timeapproximately 4 months
Work-upSaturated solution of 6 in aqueous 30% ammonia subjected to slow vapour diffusion of ethanol; orange-yellow needles obtained.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecomplex 6saturated solutionp006 / article p.754 · Synthesis of compounds
Additiveaqueous ammonia30%p006 / article p.754 · Synthesis of compounds
Solventethanolvapour diffusionp006 / article p.754 · Synthesis of compounds
Partial recipeSource: Main

Route 4: Other

p006 / article p.754 · Synthesis of compounds

Metal precursorspowdery complex 6, 0.250 g (1.1 mM reported)
Linker precursorstetraazamacrocyclic ligand 2, 0.395 g (1.5 mM reported)
Solvents10 mL acetonitrile; mother liquor crystallisation
AdditivesP2O5 and H2SO4 desiccators
Atmosphereambient desiccator conditions
Temperatureambient
Timeseveral days
Work-upDissolve 6 with ligand 2 in acetonitrile under stirring; filter yellow-brown solution; leave over P2O5 for several days; filter and dry microcrystalline brown complex over H2SO4. X-ray blocks appeared from mother liquor.
Activationdesiccator drying over H2SO4
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcepowdery 60.250 g (1.1 mM reported)p006 / article p.754 · Synthesis of compounds
Linkertetraazamacrocyclic ligand 20.395 g (1.5 mM reported)p006 / article p.754 · Synthesis of compounds
Solventacetonitrile10 mLp006 / article p.754 · Synthesis of compounds
AdditiveP2O5desiccator drying agentp006 / article p.754 · Synthesis of compounds
AdditiveH2SO4desiccator drying agentp006 / article p.754 · Synthesis of compounds
Partial recipeSource: Main

Route 5: Other

p004 / article p.752 · Synthesis of compounds - Cyanoxime ligand, 1

Metal precursorsNaH(1)2 / compound 4
Linker precursorsamide-cyanoxime acid salt precursor
Solventswater; ether extraction; acetone-water crystallisation
Additivesdilute HCl; solid NaCl
Work-upAcidify aqueous NaH(1)2 to pH approximately 3, saturate with NaCl, extract by ether; crystallise from acetone-water.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNaH(1)2Not specifiedp004 / article p.752 · Synthesis of compounds - Cyanoxime ligand, 1
Aciddilute HCldilutep004 / article p.752 · Synthesis of compounds - Cyanoxime ligand, 1
Additivesolid NaClsaturation of solutionp004 / article p.752 · Synthesis of compounds - Cyanoxime ligand, 1
Solventetherextraction solventp004 / article p.752 · Synthesis of compounds - Cyanoxime ligand, 1
Complete recipeSource: Main

Route 6: Other

p004 / article p.752 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5

Metal precursorsNaNO2, 9.84 g (0.142 mol)
Linker precursors2-cyano-acetamide, 10.0 g (0.119 mol)
Solvents120 mL H2O
Additivesglacial acetic acid, 10.2 mL (10.7 g, 0.178 mol)
Atmosphereinert gas protection
Temperatureapproximately 0 C; additional precipitation at +4 C
Time12 h plus 24 h additional precipitation at +4 C
Oxidant / reductantnitrosation by sodium nitrite under acidic conditions
Work-upYellow needles precipitated; extra salt precipitated in flask at +4 C.
Scalability context10 g scale reported; total yield 93% after additional precipitation.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linker2-cyano-acetamide10.0 g (0.119 mol)p004 / article p.752 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
OtherNaNO29.84 g (0.142 M reported)p004 / article p.752 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
SolventH2O120 mLp004 / article p.752 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
Acidglacial acetic acid10.2 mL (10.7 g; 0.178 mol) · glacialp004 / article p.752 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
Partial recipeSource: Main

Route 7: Other

p005 / article p.753 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5

Metal precursorsCsOH in ethanol
Linker precursorsprotonated ligand 1 in ether solution
Solventsether; ethanol; dry cold ethanol wash; ether wash
Oxidant / reductantbase deprotonation
Work-upYellow-orange precipitates filtered, washed with 4-8 mL dry cold ethanol, then ether, and dried under vacuum.
Activationvacuum drying
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Linker1ether solutionp005 / article p.753 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
BaseCsOH / MOHethanol solutionp005 / article p.753 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5
Solventdry cold ethanol4-8 mL washp005 / article p.753 · Synthesis of compounds - Anionic cyanoxime ligand in compounds 4 and 5