Jeramie J. Adams

Homoleptic Tris-Diphosphine Re(I) and Re(II) Complexes and Re(II) Photophysics and Photochemistry

The ligand-to-metal charge transfer state (LMCT) of [(dmpe)3Re](2+) (dmpe = 1,2-bis(dimethylphosphino)ethane) has been demonstrated to be a potent oxidant (E(0)(Re(2+*)/Re(+)) = 2.61 V vs standard calomel electrode). This complex has been traditionally prepared by nontrivial routes in low yields, and very little has been achieved in optimizing the ground state and emission energy properties of the general class of complexes [(PP)3Re](2+) (PP = chelating diphosphine) through phosphine modification. Improved syntheses for Re(I) tris-homoleptic diphosphine complexes [(PP)3Re](+) (PP = 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(diethylphosphino)ethane (depe), bis(dimethylphosphino)methane (dmpm), bis(diphenylphosphino)methane (dppm), Me2PCH2PPh2, 1,3-bis(dimethylphosphino)propane (dmpp), or 1,2-bis(dimethyl-phosphino)benzene (dmpb)) were achieved by single-pot reactions exploiting the reducing potential of the phosphines when reacted with Re(V) oxo-complexes in 1,2-dichlorobenzene at 160-180 °C. Single-electron chemical oxidation of [(PP)3Re](+) yields luminescent Re(II) analogues; appropriate use of Ph3C(+), Cp2Fe(+), or (4-BrC6H4)3N(+) B(C6F5)4(-) salts produced [(PP)3Re](2+) complexes in good yields. Crystallographic trends for the Re(+)/Re(2+) pairs show significantly lengthened Re(2+)-P bonds for [(PP)3Re](2+) relative to the corresponding [(PP)3Re](+) system. The redox and luminescence behavior of the complexes indicates the luminescence is from a ligand P(σ)-to-metal (Re(dπ)) charge transfer ((2)LMCT) state for all the complexes. Structured luminescence at 77 K is postulated to originate from relaxation of the (2)LMCT state into two spin-orbit coupled states: the ground state and a state ∼ 3000 cm(-1) above the ground state. The excited-state reduction potential (Re(II*/I)) for [(depe)3Re](2+) was determined from the free energy dependence of luminescence quenching rate constants. Yields for formation of charge separated ions were determined for three of the complexes with a variety of electron donors. Despite favorable electrostatics, no charge separated ions were observed for radical ion pairs for which the energy of back electron transfer exceeded 1.1 V.

Unexpected formation of ruthenium(II) hydrides from a reactive dianiline precursor and 1,2-(Ph2P)2-1,2-closo-C2B10H10.

Reaction of the new precursor cis, trans-Ru(cod)(anln)2Cl2 with the diphosphine 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane (o-dppc) unexpectedly results in two new ruthenium(II) hydrides, trans-Ru(o-dppc) 2(H)Cl and the neutral, five-coordinate complex Ru(o-dppc)(nido-dppc)(H), depending upon the reaction conditions [anln is aniline and nido-dppc is 7,8-(Ph2P)2C2B9H10(-)]. Chloride abstraction from trans-Ru(o-dppc)2(H)Cl leads to another five-coordinate hydride, [Ru(o-dppc)2(H)](+), which is isolated as either a triflate or hexafluorophosphate salt. On the basis of labeling and reactivity studies, the source of the hydride appears to be the cod ligand.

Acceptor pincer Ru(II) chemistry

A series of new acceptor pincer Ru(II) complexes are reported. The carbonyl complex ((CF(3))PCP)Ru(CO)Cl(2)(-)Et(3)NH(+) is obtained from the reaction of (CF(3))PCPH with [(cod)Ru(μ-Cl)(2)](n). Chloride displacement with (CF(3))PCPH, CO, PPh(3), or C(2)H(4) gave complexes of the type ((CF(3))PCP)Ru(CO)(L)Cl, or in the case of (CF(3))PCPH, the bridged dimeric complex [((CF(3))PCP)Ru(CO)Cl](2)(μ-(CF(3))PCPH). Chloride abstraction from ((CF(3))PCP)Ru(CO)(L)Cl, L = CO or PPh(3) by (Et(3)Si)(2)(μ-H)(+)B(C(6)F(5))(4)(-) followed by Et(3)N addition produced ((CF(3))PCP)Ru(CO)(L)(H) products. Reaction of cis-((CF(3))PCP)Ru(CO)(2)Cl with (Et(3)Si)(2)(μ-H)(+)B(C(6)F(5))(4)(-) in the presence of excess CO afforded ((CF(3))PCP)Ru(CO)(3)(+). The reaction of (CF(3))PCPH with (PPh(3))(3)Ru(H)(O(2)CR) (R = Me or Ph) produced the corresponding carboxylate complexes ((CF(3))PCP)Ru(PPh(3))(O(2)CR).

Chemo-mechanical Characterization of Bitumen Binders with the Same Continuous PG–Grade

Chemo-mechanical analysis tools were used to provide plausible reasons behind different binder properties that are not well captured by the conventional Superpave PG-grading system. In this study, six binders were divided in two groups based on their continuous PG-grades. The binder matrix includes: two SBS modified binders, one air blown bitumen, one bitumen with high wax content and two other unique binder blends. Although the binders in each group have the same continuous PG-grades based on AASHTO M320, they exhibit very different low-temperature performance based on the binder relaxation ΔTc index, and they have different upper PG performance according to MSCR testing and AASHTO MP19, which takes into account both traffic load and climate conditions. Based on the results, high apparent molecular weight waxes appear to lead to poor low-temperature cracking and lower molecular weight waxes lead to poor rutting performance. Meanwhile incompatible polymer modification seems to lead to poor rutting and cracking performance relative to unmodified binders or even air blown binder.