TRANSITION-METAL CHEMISTRY OF MAIN-GROUP HYDRAZIDES .5. FUNCTIONALIZATION OF METHYLHYDRAZINE WITH ALKYL ALKOXY GROUPS AND ARYL ARYLOXY-SUBSTITUTED PHOSPHORUS(V) OXIDES AND SULFIDES - 1ST EXAMPLES OF BIDENTATE INTERACTIONS OF R2P(E)(NMENH2) (R=OME, OET, OPH, PH E=S, O) WITH PD(II) - X-RAY STRUCTURE OF (MEO)2P(S)NMENH2PDCL2

The reactions of alkoxy-, aryloxy-, and aryl-substituted phosphorus mo nochlorides (R2P(E)Cl: R = OCH3, E = S; R = OC2H5, E = S; R = OC6H5, E = O; R = C6H5, E = O) with methyl hydrazine yielded the new monophosp horus hydrazides (R2P(E)NMeNH2: R = OCH3, E = S (1); R = OC2H5, E = S (2), R = OC6H5, E = 0 (3); R = C6H5, E = O (4)) in good yields. The mo nophosphorus hydrazides 1-4 reacted smoothly with PdCl2(PhCN)2 at 25-d egrees-C to give the new cyclopalladaphosphohydrazides R2P(E)NMeNH2.Pd Cl2 (R = OCH3, E = S (5); R = OC2H5, E = S (6); R = OC6H5, E = O (7); R = C6H5, E = O (8)) in good yields as air-stable crystalline solids. The chemical constitutions of 1-4 and 5-8 were established by complete NMR (H-1 and P-31) spectroscopic and C, H, N, and Cl analysis data. T he structure of 5 was further confirmed by X-ray diffraction study. Cr ystal data for 5: monoclinic, space group C2/c, with a = 25.029(9) ang strom, b = 10.2800(10) angstrom, c = 9.167(3) angstrom, beta = 104.750 (10)-degrees, and Z = 8. The structure was solved by direct methods an d was refined to R = 0.035.