Degree Name
Master of Science (MS)
Semester of Degree Completion
1992
Thesis Director
Richard L. Keiter
Abstract
In this work we have explored reactions of coordinated diphenylvinylphosphine with coordinated diphenylphosphine. Starting materials, (OC)4FePPh2CH=CH2, trans- (OC)3Fe(PPh2CH=CH2)2, (OC)4FePPh2H, and trans- (OC)3Fe(PPh2H)2 were successfully prepared from known procedures. The bimetallic complex, (OC)4FePPh2CH2CH2PPh2Fe(CO)4, was obtained in 69% yield from the reaction of ((OC)4FePPh2CH=CH2 with (OC)4FePPh2H. The trimetallic complex, (OC)4FePPh2CH2CH2PPh2Fe(CO)3PPh2CH2CH2PPh2Fe(CO)4, was obtained from the reaction of (OC)4FePPh2CH=CH2 with trans- (OC)3Fe(PPh2H)2, in 51% yield. The bimetallic and trimetallic complexes were prepared in THF by employing potassium tert-butoxide as a base catalyst. All of these complexes were characterized by phosphorus-31 NMR and by IR spectroscopy.
It was not possible to prepared the trimetallic complex from trans- (OC)3Fe(PPh2CH=CH2)2 with (OC)4FePPh2H. Nor was it possible to induce polymerization from the reaction of trans- (OC)3Fe(PPh2CH=CH2)2 with trans- (OC)3Fe(PPh2H)2. In each case the diphenylvinylphosphine complex was recovered unchanged, but the diphenylphosphine complex decomposed to unidentified products. It became evident that whereas (OC)4FePPh2CH=CH2 undergoes reaction with either Fe(CO)4PPh2H or trans-Fe(CO)3(PPh2H)2, trans-Fe(CO)3(PPh2CH=CH2)2 undergoes reaction with neither. It appear that the rate of decomposition of either diphenylphosphine complex is faster than the rate of addition to trans-Fe(CO)3(PPh2CH=CH2)2.
It was shown that phosphines react with trans-Fe(CO)3(AsPh3)2 to displace triphenylarsine in stepwise fashion. This method was used to produce the mixed ligand complex, trans-Fe(CO)3(PPh2H)(PPh2CH=CH2). It was not established whether this monomer can be polymerized in the presence of base.
Preliminary work also shows that Ph2PC≡CPPh2 reacts with trans-Fe(CO)3(AsPh3)2 by displacing triphenylarsine. This reaction shows promise as a means of producing polymers in which the Fe(CO)3 units are bridged by Ph2PC≡CPPh2.
Recommended Citation
Chen, Xi, "Iron Tricarbonyl Derivatives of Ditertiary Phosphines" (1992). Masters Theses. 2140.
https://thekeep.eiu.edu/theses/2140
