Synthese funktionalisierter tipod-Liganden: Aufbau, Veresterung und Koordinationsfähigkeit von HOCH2C (CH2PPh2)3

Bidentate and terdentate (P-N-S) complexes of a new thioether azine phosphine Z,E-PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4) with molybdenum, tungsten, or platinum

“…Treatment of 1 with [ M O ( C O ) , (~~-C~~) ] (25) (cht = cyclohepta-1,3,5-triene) in benzene solution displaced cyclohepta-l,3,5-triene to give the tricarbonylmolybdenum(0) complex 3a as yellow needles in 85% yield. The infrared spectrum of this complex showed two strong bands for v(C=O) at 1930 and 18 10 cm-', close to literature values observed for zerovalent molybdenum tricarbonyls (26)(27)(28). The ' 3~-{ '~} NMR spectrum of 3a showed three doublet resonances for the C s ligands in a 1: 1: 1 ratio.…”

Tripodal Phosphane Ligands with Novel Linker Units and Their Rhodium Complexes as Building Blocks for Dendrimer Catalysts

“…In view of the principal objective of this work, the synthesis of cationic triphos-rhodium hydrogenation catalysts attached to dendritic supports, the ligand-linker unit 9 was reacted with [Rh(COD) 2 ]BF 4 to give the Rh I complex [{HOCH 2 CH 2 OCH 2 C(CH 2 PPh 2 ) 3 }Rh(COD)][BF 4 ] (11a; Scheme 2) which was characterised by elemental analysis and 1 H, 13 C and 31 P NMR spectroscopy. The most characteristic spectroscopic feature is the doublet at δ ϭ 4.3 ppm in the 31 P NMR spectrum ( 1 J Rh,P ϭ 106.8 Hz) indicating the equivalence of all three phosphorus nuclei on the NMR time scale at 293 K. The observation of an essentially unchanged single phosphorus resonance even at Ϫ80°C is consistent with a rapid dynamic exchange, probably according to a turnstile mechanism, as was previously observed for [Rh(triphos)(COD)]PF 6 and [Ir(triphos)(COD)]PF 6 .…”

“…Solids were separated from suspensions by filtration through dried Celite or by centrifugation. The 1 H, 13 [18] benzyl 2-chloroethyl ether, [19] diphenylphosphane, [26] 3-chloro-(2,2-chloromethyl)-propan-1-ol (7), [20] 2-(2-Bromoethoxy)tetrahydropyran, [27] [(MeCN) 3 Mo(CO) 3 ], [28] [Rh(COD) 2 ]BF 4 , [29] G[0]-[Cl] 4 (12), [30] G .0 mmol) was added to a stirred suspension of finely powdered KOH (11.2 g, 200 mmol) and benzyl 2-chloroethyl ether (30.9 g, 181 mmol) in 150 mL of DMSO. The reaction mixture was stirred at 60°C for 2 h and then cooled to room temperature.…”

3-tert-Butyl-4-methyl-2-phenyl-3-(trimethylsilyloxy)oxetane and 2-(2-Benzyloxyphenyl)-3-tert-butyl-3-(trimethylsilyloxy)oxetane

“…The non-planarity can also be seen from the ring torsion angles, which are clearly different from zero [O1--C2--C3--C4 5.8(2) in (I) and -14.2(2) ° in (II)]. Previous single-crystal X-ray investigations on substituted oxetane derivatives (Seitz et al, 1994;Khan, Morris, Smith & Walsh, 1991;Morris, Smith & Walsh, 1987;George & Gilardi, 1986;Hospital, Leroy, Bats & Moulines, 1978;Holan, Kowala & Wunderlich, 1973) show that the puckering angles can vary from 0 to 22.9 (2) °. Furthermore, the crystal structure of unsubstituted oxetane has been determined at temperatures of 90 and 140 K (Luger & Buschmann, 1984); the ring exhibits a non-planar structure with puckering angles of 10.7(1) ° at 90K and 8.7(2) ° at 140 K.…”