Dale C. Smith

Ruthenium(II) chemistry of phosphorus-based ligands, Ph2PN(R)PPh2 (R=Me or Ph) and Ph2PN(Ph)P(E) Ph2 (E=S or Se). Solution thermochemical study of ligand substitution reactions in the Cp′RuCl(COD) (Cp′=Cp, Cp*; COD=cyclooctadiene) system

Abstract The enthalpies of reactions of Cp′RuCl(COD) (Cp′=Cp, Cp*; COD=cyclooctadiene) with bis(phosphino)amines of the type Ph 2 PN(R)PPh 2 (R=Me 1 or R=Ph 2 ) and the monochalcogen derivatives Ph 2 PN(Ph)P(E)Ph 2 (E=S 3 or Se 4 ) leading to the formation of Cp′RuCl(PNP) and Cp′RuCl{PNP(E)} complexes, respectively, have been measured by anaerobic solution calorimetry in THF at 30°C. These reactions are clean and quantitative. The synthesis and characterization of new organoruthenium complexes is reported. Comparisons with enthalpy data in this two related organoruthenium systems and other similar organometallic systems are also presented.

Synthetic and thermochemical studies of fluorinated tertiary phosphine ligands R2PRf [R=Cy, Ph, iPr; Rf=CH2CH2(CF2)5CF3] in an organoiron system

Abstract The fluorinated phosphine ligands [PR 2 R f (R=Cy ( 2 ); i Pr, ( 3 ); Ph, ( 4 ); R f =CH 2 CH 2 (CF 2 ) 5 CF 3 ] react with Fe(CO) 3 (BDA) ( 1 ) (BDA=(C 6 H 5 )CH=CHC(O)CH 3 , benzylideneacetone) to yield the corresponding Fe(CO) 3 (PR 2 R f ) 2 (R=Cy, ( 5 ) i Pr, ( 6 ) Ph, ( 7 )) complexes. Infrared studies on the carbonyl complexes and solution calorimetry studies of the reaction of 1 with 2 , 3 and 4 have been performed to quantify the donor strength of this series of ligands.