Master of Science (MS)
Semester of Degree Completion
Richard L. Keiter
A tungsten-mercury bimetallic complex [(CO)4W(PPh2CH2CH2PPh2)2HgCl2]n has been synthesized from the reaction of trans-(CO)4W(η1-PPh2CH2CH2PPh2)2 and HgCl2. The value of n has not been determined due to the insolubility of the complex. The anologous reaction with HgI2 gave an insoluble, uncharacterizable complex, which best corresponds to (CO)4W(PPh2CH2CH2PPh2)2Hg2I4.
The geometry about tungsten in [(CO)4W(PPh2CH2CH2PPh2)2HgCl2]n is cis as shown by P-31 nmr (JW-P= 230.0 and JHg-P= 4420 Hz) and by infrared spectroscopy. Isomerization of trans-(CO)4W(η1-PPh2CH2CH2PPh2)2 occurred when it reacted with HgCl2. The energy barrier for isomerization is undoubtedly low and the process was probably induced as a result of steric pressure.
The starting material,trans-(CO)4W(η1-PPh2CH2CH2PPh2)2, was prepared from the reaction of trans-(CO)4W(PPh2CH=CH2)2 and PPh2H in the presence of base. The reaction of W(CO)6 with PPh2CH=CH2 in n-butanol in the presence of NaBH4 gave trans-(CO)4W(PPh2CH=CH2)2 (57 % yield).
Abdullah, Zakariah, "Bimetallic Complexes of Tungsten and Mercury" (1985). Masters Theses. 2738.