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)
Hj. Plinta et al., 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), Zeitschrift fur Naturforschung. B, A journal of chemical sciences, 49(1), 1994, pp. 100-110
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.