335413-77-9

Upstream product

• 109-99-9 tetrahydrofuran 
• 14040-11-0 tungsten hexacarbonyl 
• 438037-43-5 (2-methoxyphenyl)bis(3,5-dimethylpyrazol-1-yl)methane 
• 122606-06-8 1-(phenylthio)methyl-3,5-dimethyl-1H-pyrazole 

Relevant academic research and scientific papers

Reactivity of bis(pyrazol-1-yl)methanes functionalized by 2-hydroxyphenyl and 2-methoxyphenyl on the methine carbon atom with W(CO)5THF

Reactions of 2-hydroxyphenyl and 2-methoxyphenylbis(pyrazol-1-yl)methanes as well as 2-hydroxyphenyl and 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl) methanes with W(CO)5THF have been carried out. Heating 2-hydroxyphenylbis(pyrazol-1-yl)methane (L1) with W(CO) 5THF in THF at reflux yielded complex (L1)W(CO) 4.L1, while similar reaction of 2-hydroxyphenylbis(3,5- dimethylpyrazol-1-yl)methane (L2) with W(CO)5THF resulted in the cleavage of a Csp3-N bond to generate 1,2-bis(2-hydroxyphenyl) -1,2-bis(3,5-dimethylpyrazol-1-yl)ethane (L) and pyrazole derivative W(CO) 5(3,5-Me2PzH) (Pz = pyrazol-1-yl). These two fragments were connected together through strong O...H-N and O-H...N hydrogen bonds to form complex L.[W(CO)5(3,5-Me2PzH)]2. The analogous results were observed in the treatment of 2-methoxyphenylbis(pyrazol- 1-yl)methane (L3) with W(CO)5THF, which gave product L′.[W(CO)5(PzH)]2 (L′ = 1,2-bis(2- methoxyphenyl)-1,2-bis(pyrazol-1-yl)ethane) as well as certain amount of complex (L3)W(CO)4. In addition, during the reaction of 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (L4) with W(CO)5THF, partial decomposition reactions took place to yield complexes (L4)W(CO)4 and W(CO)5(3,5-Me 2PzH), but no hydrogen bond was found between these two moieties.

The modification of ArSCH2(3,5-Me2Pz) (Ar = phenyl or 2-pyridyl, Pz = pyrazol-1-yl) by organotin group and related reactions

Reaction of 1-arylthiomethyl-3,5-dimethylpyrazole [ArSCH 2(3,5-Me2Pz), Ar = phenyl or 2-pyridyl, Pz = pyrazol-1-yl] with Mo(CO)6 produces complexes ArSCH2(3,5-Me 2Pz)Mo(CO)4, while similar reaction with W(CO)6 yields analogous complexes ArSCH2(3,5-Me2Pz)W(CO) 4 and concomitant desulfurized complex (3,5-Me2PzH)W(CO) 5 in the reaction of PhSCH2(3,5-Me2Pz). Succedent treatment of complexes PhSCH2(3,5-Me2Pz)M(CO) 4 with SnCl4 gives heterobimetallic complexes PhSCH 2(3,5-Me2Pz)M(CO)3(Cl)(SnCl3) (M = Mo or W) in good yields. ArSCH2(3,5-Me2Pz) act as S,N chelating bidentate ligands through the sulfur and the pyrazolyl nitrogen atoms in the aforementioned complexes. The modification of ArSCH2(3,5- Me2Pz) by organotin group at the methylene group has been successfully carried out, which yields functionalized ligands Ph 3SnCH(SAr)(3,5-Me2Pz). Markedly different reactions are observed, upon treatment of Ph3SnCH(SPh)(3,5-Me2Pz) and Ph3SnCH(SPy)(3,5-Me2Pz) (Py = 2-pyridyl) with W(CO) 5THF. The former yields complex Ph3SnCH(SPh)(3,5-Me 2Pz)W(CO)4, as well as PhSCH2(3,5-Me 2Pz)W(CO)4 with a partial loss of the organotin moiety, while no reaction takes place in the latter. In addition, reaction of Ph 3SnCH(SPy)(3,5-Me2Pz) with Mo(CO)6 results in the oxidative addition reaction of the Sn-Csp3 bond to the molybdenum(0) atom to yield novel heterometallacyclic complex CH(SPy)(3,5-Me2Pz)Mo(CO)3SnPh3, in which [(2-pyridyl)thiomethyl](3,5-dimethylpyrazol-1-yl)methide acts as a tridentate κ3-[N,C,N] chelating ligand through the carbon atom, the pyrazolyl and the pyridyl nitrogen atoms, as the sulfur atom does not coordinate to the molybdenum atom anymore. Interestingly, treatment of this heterometallacyclic complex with P(OR)3 (R = Ph or Et) gives rise to the isomerization of the C-S bond to the C-N bond, generating the thione-S coordinated complex CH(NC4H4C = S)(3,5-Me 2Pz)Mo(CO)2(P(OR)3)SnPh3, in which the ligand binds in a novel tridentate, monoanionic κ3-[N,C,S] chelating mode to the molybdenum atom.