This review is devoted to non-hydrolytic sol-gel chemistry. During the last 25 years, non-hydrolytic sol-gel (NHSG) techniques were found to be attractive and versatile methods for the preparation of oxide materials. Compared to conventional hydrolytic approaches, the NHSG route allows reaction control at the atomic scale resulting in homogeneous and well defined products. Due to these features and the ability to design specific materials, the products of NHSG reactions have been used in many fields of application. The aim of this review is to present an overview of NHSG research in recent years with an emphasis on the syntheses of mixed oxides, silicates and phosphates. The first part of the review highlights well known condensation reactions with some deeper insights into their mechanism and also presents novel condensation reactions established in NHSG chemistry in recent years. In the second section we discuss porosity control and novel compositions of selected materials. In the last part, the applications of NHSG derived materials as heterogeneous catalysts and supports, luminescent materials and electrode materials in Li-ion batteries are described.

The mechanism of chemical vapor deposition of Cu, CU2O, CuO, and CU3N from Cu(hfacac)2-(H2O) was studied by XRD, MS, FTIR, XPS, SIMS, and NMR techniques. The molecular structure of the precursor was established by a single-crystal X-ray diffraction experiment.Crystallographic data (-165 °C): triclinic space group PI, a = 9.402(3) k,b = 11.068(3) A, c = 7.958(2) A, a = 105.71(2)°, 0 = 100.99(2)°, y = 76.27(2)°, V = 767.31 A* 123 45678, Z = 2, R = 0.0303, i?w = 0.0312. In the presence of excess water in the process gas stream, a facile release of free Hhfacac ligand from the copper complex is activated by a proton transfer from coordinated water. Ligand-mediated reduction of the metal from Cu2+ to Cu+ and from Cu+ to Cu°oxidation states occurs in the absence of an external reducing agent at temperatures of 280 and 400 °C, respectively. Evidence for this ligand-mediated reduction is seen in the presence of the two major ligand-oxidation products (CF3COOH and CFsC(OH)2-CH(OH)2) in the effluent from the deposition reaction. A labeling experiment using H2180 proved that oxygen in copper oxide films deposited from Cu(hfacac)2 onto insulating substrates is derived from water and not the hfacac ligand. As an example of benefits that can be derived from this mechanistic knowledge, we have also shown that replacing H2O with NH3 leads to the formation of CU3N.

The two new azaphosphatranes HP(RNCH,CH,),N'Cl~ (R = Et, 2c and R = i-Pr, 2d) were prepared from the corresponding (RNHCH,CH,),N and CIP(NEt,),. They were transformed into the title proazaphosphatranes 3c and 3d, respectively, with tert-BuOK. Alternatively, 3d was prepared by the transamination reaction of PCl(NMe,), with (isoPrNCH,CH,),N followed by deprotonation with tert-BuOK. Azaphosphatrane cation salts of 3d, [Z-P (iso-PrNCH,CH,),N]were obtained from the reaction of 3d with ZC1. Competitive deprotonations of azaphosphatrane cation pairs with a stoichiometric deficit of tert-BuOK in DMSO showed the order of basicity: 3e > 3d > P (MeNCH,CH,),N (3b). Compound 3d is also a more efficient catalyst for the trimerization of phenyl isocyanate to phenylisocyanurate than is 3b. A strong correlation (r = 0.996) of the transannular distance with the distance of the P from the plane of its amido nitrogens in nine compounds of the type [ZP (RNCH,CH,),N] + is observed. The molecular structure of 3d shows a P-N,, distance of 3.29 A, which is 1.8% shorter than the sum of the corresponding van der Waals radii. Crystal data for 3d: u = 9.380 (2) A, b = 11.979 (2) A, c = 16.063(3) A, = 95.62(1)", V = 1796.2(6) A3, Z = 4, space group P2,/nd R(e) = 3.62%. The molecular structure of 2d exhibits a transannular R-N,, bond of 1.95 A in a nearly undistorted trigonfl bipyramidalphosphorus. Crystal data for 2d: u = 9.143(4) A, b = 9.319(4) A, c = 11.616(3) A, GL = 87.07(3) ", = 88.64(3)", 7 = 80.62(3)", V = 972.8(6) A,, Z = 2, space group Pi, R = 3.42%.

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