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"A series of known and new seven coordinate molybdenum and tungsten complexes of tris(pyrazolyl)methane (Tpm) and substituted Tpm, [TpmM(CO)3X]+, have been synthesized. Depending on the identity of X, (bromo, iodo, hydrido) and the substitution of the Tpm ligand, substantial chemical shift differences are observed for the hydrogen on the central carbon of the Tpm ligand. Factors impacting the chemical shift of the hydrogen on the central carbon of the Tpm ligand, such as the electron donating ability of the Tpm ligand and the electronegativity of the additional ligand on the metal, will be discussed"--Unnumbered leaf 1.
"Tpm^Ph, or tris(3-phenylpyrazolyl)methane reacts with tungsten hexacarbonyl to form the ligand-metal complex tris(3-phenylpyrazolyl)methane tungsten tricarbonyl, or Tpm^PhW(CO)3. The further complexes of Tpm^PhW(CO)3 and Tpm^PhMo(CO)3 are not known. This project aims to explore how the addition of a phenyl substituent to the pyrazole ring on Tpm impacts the synthesis of [Tpm^PhW(CO)3I]+X- and [Tpm^PhW(CO)3H]+X-. The inclusion of this phenyl substituent may impact the possible hydrogen bonding of then hydrogen contained in the carbon-hydrogen bond. This work aims to explore the extent of hydrogen-bonding of the carbon-hydrogen bond of the Tpm^Ph ligand in cationic metal complexes"--Leaf 1.
"The scorpionate ligand tris(pyrazolyl)borate (Tp) has contributed to the understanding of coordination and organometallic chemistry and has proven to be useful in the synthesis of metalloprotein models. Studies focusing on the similar ligand, tris(pyrazolyl)methane (Tpm), have recently been made possible with improved synthetic techniques. Characterization of the Tpm ligand and its metal derivatives, [TpmW(CO)3L]+ and [TpmMo(CO)3L]+, unveiled unexpected activity in the 1H NMR chemical shift of the methane hydrogen after the coordination of a seventh ligand. The more electronegative the seventh ligand was, the more downfield the chemical shift appeared. Various analogs of Tpm have since been synthesized that substitute methyl groups on different positions of the pyrazolyl rings and the effect of these substitutions on the methane hydrogen was examined. This work successfully synthesized an analog of Tpm(4-methyl) and its metal complexes of Tpm(4-methyl)W(CO)3 and Tpm(4-methyl)Mo(CO)3. The reactivity of Tpm(4-methyl)M(CO)3 (M = W or Mo) was observed and FTIR, 1H NMR, and 13C NMR were used for the characterization of [Tpm(4-methyl)M(CO)3L]+[X]- (L = H, I, or Br; X = counterion). The chemical shift of the methane hydrogen was further examined and determined to follow the same trend seen in the previously reported Tpm metal complexes"--Leaf 1.