Earlier the trimethylsilyldimethylphosphane Me 2 PSiMe 3 (I) was utilized for the substitution of fl uorine atom with PMe 2 groups in polyfl uoroarenes C 6 F 5 X (X = H, F, Cl, CF 3 , etc.) and pentafl uoropyridine [1,2], and also in 1,2,3-and 1,3,5-trifl uoro-, 1,2-and 1,3-difl uorobenzenes [3,4]. In this study the reagent was applied to the preparation of benzene-1,2-diylbis(dimethylphosphane) (II) and its new analog, 3-fl uorobenzene-1,2-diylbis(dimethylphosphane) (III), chelating ligands for transition metal complexes as had been described for phosphane II [5,6].The reaction of ortho-difl uorobenzene with exess phosphane I at relatively high temperature led to the formation (in keeping with the data of 19 F and 31 P NMR spectra) a mixture of dimethyl(2-fl uorophenyl)phosphane (32%) [4] and diphosphane II (68%) isolated in 60% yield (Scheme 1). Lately diphosphane II was synthesized from dimethyl-(2-chlorophenyl)phosphane by metallation with lithium followed by the treatment with dimethylchlorophosphane [5] of by alkylation of 1,2-diphosphanobenzene sodium salts with methyl iodide [7] in 11 and 68% yield respectively.Phosphane IV obtained formerly by phosphanedebromination of 2,6-F 2 C 6 H 3 Br with lithium dimethylphosphide (V) [8] reacted with phosphane I under milder conditions affording in 96% yield diphosphane III that was isolated in 57% yield (path a, Scheme 2).Phosphane I in contrast to phosphide V reacts with 2,6-F 2 C 6 H 3 Br to give 92% of (2-bromo-3-fl uorophenyl) dimethylphosphane (VI) and 7% of phosphane IV (Scheme 2, path b). The main product was isolated in 62% yield. The discovered difference in the results of the reaction between 2,6-F 2 C 6 H 3 Br and reagents I and V is probably due to the difference in the mechanism of reactions involving nucleophiles I and V: With Me 2 PLi this is the mechanism S RN 1 initiated by the electron transfer from the nucleophile to the substrate (cf. [8]), and in the process with Me 2 PSiMe 3 it is synchronic mechanism A N D N apparently observed in its reactions with di-and trifl uorobenzenes [4]. In this respect it is illustrative that the ratio (VI)-(IV) equal 13:1 indicates a weaker element-effect compared to reactions S N Ar: In the products of reaction between bromofl uorobenzenes with sodium methylate in a mixture DMSO-MeOH the Br -ions have not been found even in traces [9]. Probably the relatively low selectivity with respect to the nature of the substituted halogen is characteristic of the A N D N mechanism combining in a cerScheme 1.