Iminophosphorane derivatives of s-triazine and tri-s-triazine, C 3 N 3 (NQPCl 3 ) 3 (1), [H 2 C 3 N 3 NH 2 (NQPPh 3 ) 2 ]Br 2 (2), [HC 3 N 3 NH 2 (NQPPh 3 ) 2 ]Br (3), C 6 N 7 (NQPCl 3 ) 3 ( 5), [HC 6 N 7 (NQPCl 3 ) 3 ]Cl (6) were obtained by the Kirsanov reaction of melamine (1-3) and melem (5 and 6) with halogenated phosphorus compounds. The products were characterized by FTIR and solution NMR spectroscopy as well as by single-crystal X-ray diffraction. Additionally, in order to investigate the electron density distribution in the s-triazine or s-heptazine systems combined with the phosphinimine group, and to understand the influence of protonation on the triazine and heptazine moieties, quantum chemical analyses of compounds 2, 3, 5 and 6 were performed. Furthermore, by reaction of 5 with phenol the compound C 6 N 7 (NQP(OPh) 3 ) 3 ( 7) was obtained. Its potential application as a flame retardant was examined by the UL 94 flammability test.Scheme 1 s-Triazine and s-heptazine structural motifs and some of their derivatives.Scheme 2 General structure of the iminophosphoranes.

lead to a large variety of products due to the competition of substitution reactions and ring contractions. The resulting new compounds were characterized by elemental analyses, NMR spectroscopy, and single crystal X-ray structure analyses.

Novel heterometallic silazane complexes were synthesized by the reaction of 1‐lithio‐2,2,4,4,6,6‐hexamethylcyclotrisilazane Li(HMCTS)H2 with the tetrachloride salts of titanium and germanium as well as by the reaction of 1,1,3,3,5,5‐hexamethylcyclotrisilazane H3(HMCTS) with tin tetrachloride and excess triethylamine. The products [H3(DMCHS)TiCl] (1), [H3(DMCHS)GeCl] (2), and [H3(DMCHS)SnCl] (3) {H3(DMCHS) = 2,2,4,4,6,6,8,8,10,10,12,12‐dodecamethylcyclohexasilazane‐1,5,9‐triido} were characterized by 1H‐, 13C‐, 14N‐, and 29Si NMR spectroscopy, elemental analyses and single‐crystal X‐ray structure analyses. The complexes have a surprising and interesting structure, that of a new dodecamethylcyclohexasilazane system with the Ti, Ge, or Sn atom in the center. These metal atoms are coordinated by one chlorine atom and three nitrogen atoms. The metal centers are part of three six‐membered hetero‐silazane rings. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The stepwise reaction of the Si-Cl functions of 1,1,2,2-tetrachlorodimethyldisilane with RMgBr using the diethylamino unit as protecting group enables the synthesis of disilanes Si 2 Me 2 R x Cl 4−x , bearing one to four olefinic substituents (R = vinyl, α-allyl and ethynyl). The catalyst free hydroboration of such molecules represents a convenient way to prepare boron containing chlorodisilanes. 9-BBN exhibits a very high regioselectivity in the hydroboration of vinyl-, allyl-or ethynyldisilanes. In case of the ethynyl group, the hydroboration of 1,1,2-trichloro-2-ethynyldimethyldisilane and 1,2-dichloro-1,2-diethynyldimethyldisilane by the twofold addition of the 9-BBN in two separate steps was confirmed by NMR spectroscopy.