1,3-DIMETHYL-1,3-DIAZA-2-R-5,6-BENZO-2-LA MBDA(3)-PHOSPHORINAN-4-ONES(R=F, ME(2)N,2-METHYLPIPERIDINO, MEC(-O)NH-) AS LIGANDS IN TRANSITION-METAL COMPLEXES - SYNTHESIS AND STRUCTURE OF DICHLORO-PLATINUM(II)- AND TETRACARBONYL-METAL(0) COORDINATION-COMPOUNDS (METAL=CR,MO AND W)

diaza-2-fluoro-5,6-benzo-1,3,2-phosphorinane-4-one (1) reacted with (C OD)PtCl2, (COD = 1,5-cyclooctadiene) or K2PtCl4 to give the cis-dichlo ro-platinum(II) complex (2). The reactions of 1 with the tetracarbonyl norbornadiene derivatives of Cr, Mo and W furnished the complexes 3-6 . In the case of the chromium and tungsten complexes the trans-isomers 3 and 6 were formed, due to a cis-tmns-isomerization. Room temperatur e and low temperature P-31 NMR spectra of a mixture of 5 and 6 show no significant temperature dependence of the cis-trans equilibrium. The reaction of 1 with the pentacarbonyl tetrahydrofuran derivative of W l ed to the product 7. The spirophosphoranes 8 and 9 were obtained in lo w yields. The analogous reactions of 10, 15 and 20 with (COD)PtCI, and the tetracarbonyl norbornadiene derivatives of Cr and Mo furnished th e coordination compounds 11-14, 16-18, 21 and 23. In the case of all c hromium complexes only the trans-isomers 11, 16 and 21 were formed, wh ereas in the case of molybdenum cis-trans-isomer mixtures 12 and 13, a s well as 17 and 18 were obtained. An attempt to obtain the cis-isomer of the molybdenum complex 22 failed. In the case of platinum the expe cted cis-complexes 14 and 23 were formed, while the attempted synthesi s of 19 was unsuccessful. All these results are interpreted in terms o f both steric and electronic factors. The ligands 1, 10, 15 and 20 coo rdinate via phosphorus. The validity of the concept of hard and soft a cids and bases (HSAB) was confirmed. The characterization of 2-7, 11-1 4, 16-18, 21 and 23 rests, especially, on their H-1, C-13 and P-31 NMR spectra, and their mass and infrared spectra. (31)p-(31)p coupling co nstants (2)J(PP) for the cis-coordinated complexes 4, 5 and 14 involvi ng two equivalent phosphorus ligands are also reported.