The concept of managing and adjustment of friction between the wheel and rail has a long history within the operation of railways systems. In the past, adjustment/management has been limited to gauge face lubrication and the use of sanding equipment. The introduction of the top of rail (TOR) friction modifier (FM) over the last 20 years now allows for the modification of the friction at the top of rail -wheel tread interface. This paper focusses on the concept of TOR friction adjustment. Recent developments have led to a new generation of products, defined here as, TOR lubricants (oil and/or grease-based) and hybrid materials (oil/water mixtures), which are non-drying or slow drying. Definitions and functional difference are detailed and contrasted with that of the water-based drying FM. The water-based TOR FM once applied rapidly dries, mixes with the existing third-body layer, and allows for the accommodation of shear displacement. TOR lubricants and hybrid materials rely on mixed boundary layer lubrication, contrary to application of the water-based TOR FM. It has been shown that the adhesion level is highly influenced by the lubricant application rates. The risks and benefits (lateral force reduction, corrugation mitigation, and impact on energy consumption and influence on rolling contact fatigue) are discussed for all product classifications. However, a lack of data exists for the TOR lubricants especially in the area of rolling contact fatigue where laboratory studies have identified the possibility of crack interaction. Whilst it can be seen that TOR lubricants have the ability to provide similar benefits to that of a water-based FM, they exhibit a strong dependency on the application rate which may lend itself to adhesion and RCF issues. Further work is recommended in this area.

The direct synthesis of yttrium amidate complexes using the simple reaction of amide proligands and Y(N(SiMe3)2)3 results in the high-yielding preparation and isolation of crystalline, monomeric materials. The complex, tris(N-2',6'-diisopropylphenyl(naphthyl)amidate)yttrium mono(tetrahydrofuran) (4), was structurally determined to be a 7-coordinate C1 symmetric structure, maintaining one bound tetrahydrofuran molecule. Compound 4 (C12H17[NCO]C10H7)3Y(C4H8O) crystallized in the monoclinic space group P2(1)/c with a = 13.7820(11) A, b = 33.598(3) A, c = 16.0575(12) A, alpha = 90 degrees, beta = 98.762(3) degrees, gamma = 90 degrees, Z = 4. Solution phase NMR spectroscopic characterization of this same complex showed a highly symmetric species, consistent with a fluxional coordination environment for these compounds. Preliminary studies into the initiation of epsilon-caprolactone ring-opening polymerization using these complexes indicate high activity, producing high molecular weight polymer.

A high-yielding synthetic route is disclosed for yttrium bis-and mono(amidate) complexes using the reaction of amide proligand and Y(N(SiMe 3 ) 2 ) 3 starting materials. The structure, bonding, and solution phase characterization data for this new class of complexes are presented. The modular nature of the amidate ligand allows for easy addition of electron-withdrawing CF 3 groups in the ligand backbone to tune electronic properties of the resulting precatalysts. The amidate ligands in the bis(amidate) complexes were found to be highly fluxional on the NMR time scale, while the mono-(amidate) yttrium complex required heating to 110 °C before ligand redistribution was observed. Three bis(amidate) complexes with differing electronic properties and one mono(amidate) complex have been used as precatalysts for hydroamination using a wide range of aminoalkene substrates. Bis-(amidate) complexes bearing the more electron-withdrawing amidate ligands were found to be the most active precatalysts for intramolecular alkene hydroamination.

While B(C(6)F(5))(3) forms the adducts (CH(2))(4)CO(2)B(C(6)F(5))(3)1 and (CHMeCO(2))(2)B(C(6)F(5))(3)7 with δ-valerolactone and lactide, the frustrated Lewis pairs derived from B(C(6)F(5))(3) and phosphine or N-bases react with lactone to effect ring opening affording zwitterionic species of the form L(CH(2))(4)CO(2)B(C(6)F(5))(3) (L = tBu(3)P 2, Cy(3)P 3, C(5)H(3)Me(3)N 4, PhNMe(2) 5, C(5)H(6)Me(4)NH 6) while reaction with rac-lactide results in ring contraction to give salts [LH][OCCHMeCO(2)(CMe)OB(C(6)F(5))(3)] (L = tBu(3)P 8, Cy(3)P 9, C(5)H(3)Me(2)N 10, C(5)H(6)Me(4)NH 11). The mechanistic implications of these reactions are discussed.

Preparation of a N-ferrocenyl-amidinate complex was achieved by employing (TMEDA)Li[(CpFeC(5)H(4))NC(Ph)NSiMe(3)] (1) to prepare Cp*Zr[(CpFeC(5)H(4))NC(Ph)NSiMe(3)]Cl(2) (2). Complex 2 exhibited poor polymerization activity and thus a series of C-ferrocenyl bis(amidinate) complexes of the type M(L)(2)Cl(2) (M = Zr, 4; M = Ti, 5; L = (CyNC(CpFeC(5)H(4))NCy) were synthesized via reaction of ferrocenyl-amidine, H(L) and M(NMe(2))(2)Cl(2) (M = Ti, Zr·2THF). Half sandwich mono(amidinate) complexes, Cp'ZrLCl(2) (Cp' = Cp, 7; Cp' = Cp*, 8), were prepared by the reaction of Cp'ZrCl(3) with Li(L) and subsequently alkylated to give M(L)(2)Me(2) (M = Zr, 9; M = Ti, 11), CpZr(L)(CH(2)Ph)(2) (12) and Cp*Zr(L)Me(2) (10) with the appropriate alkylating agent. Abstraction of a methyl group from 7 with B(C(6)F(5))(3) and [Ph(3)C][B(C(6)F(5))(4)] proceeded cleanly to give [{CyNC(CpFeC(5)H(4))NCy}(2)ZrMe][MeB(C(6)F(5))(3)] 13 and [{CyNC(CpFeC(5)H(4))NCy}(2)ZrMe][B(C(6)F(5))(4)] 14, respectively. Similarly, the analogous CpZr and Cp*Zr derivatives LZr{CyNC(CpFeC(5)H(4))NCy}CH(2)Ph] [PhCH(2)B(C(6)F(5))(3)] L = Cp 15, Cp* 17 and [LZr{CyNC(CpFeC(5)H(4))NCy}CH(2)Ph][B(C(6)F(5))(4)] L = Cp 16, Cp* 18 were prepared. Cyclic voltammetry studies on the metal complexes containing ferrocenyl-amidinates reveal quasi reversible oxidation and reduction waves for the ferrocene/ferrocenium couple. The dichloride complexes (4-8) activated with MAO and dialkyl complexes (9,10) activated with B(C(6)F(5))(3) and [Ph(3)C][B(C(6)F(5))(4)] showed low ethylene polymerization activities.