TRANSITION-METAL CHEMISTRY OF MAIN-GROUP HYDRAZIDES .4. PHOSPHORUS HYDRAZIDO FERROCENES AS NOVEL SYNTHONS TO NEW IRON(II)-PALLADIUM(II) HETEROTRIMETALLIC ORGANOMETALLIC COMPOUNDS - SYNTHESIS AND CHARACTERIZATION OF PALLADIUM(II) CHLORIDE COMPLEXES OF FERROCENE FUNCTIONALIZED PHOSPHORUS HYDRAZIDES - SINGLE-CRYSTAL X-RAY STRUCTURES OF C2H5OP(S)(NCH3NCHCP'FECP)2 AND C2H5OP(S)(NCH3NCHCP'FECP)2.PDCL2 [CP'=C5H4, CP=C5H5]

The reactions of aryl-, alkyl-, and alkoxy-substituted phosphorus hydrazides, RP(E)(NMeNH2)2 (R = Ph, E = S, 1; R = OEt, E = S, 2; R = Ph, E = O, 3; R = Et, E = O, 4; R = Me, E = O, 5) with ferrocenecarboxaldehyde gave metallocene-functionalized phosphorus hydrazides in good yields (approximately 90-95%) as air-stable crystalline solids with the following chemical compositions: RP(E)(NMeNCHCp'FeCP)2 (R = Ph, E = S, 6; R = OEt, E = S, 7; R = Ph, E = O, 8; R = Et, E = O, 9; R = Me, E = O, 10). These ferrocenyl phosphorus hydrazides 6-10 can be used as versatile synthons to produce new heterometallic organometallic compounds. For example, 6-10 react with PdCl2(PhCN)2 at 25-degrees-C to give Fe(II)-Pd(II) trimetallic compounds RP(E)(NMeNCHCp'FeCp)2-PdCl2 (R = Ph, E = S, 11; R = OEt, E = S, 12; R = Ph, E = O, 13; R = Et, E = O, 14; R = Me, E = O, 15) in good yields. The chemical constitutions of 6-10 and 11-15 were established by complete NMR (H-1 and P-31) spectroscopic and C, H, and N analysis. As representative examples, X-ray structures of 7 and 12 have been determined. Crystal data for C2H5OP(S)(NMeNCHCp'FeCP)2, 7: orthorhombic, space group P2(1)2(1)2(1), a = 7.5556(11) angstrom, b = 10.7652(12) angstrom, c = 33.186(4) angstrom, V = 2699.3(3) angstrom3, Z = 4. The structure was solved by direct methods and was refined to R = 0.038. The structure of 12 comprises the neutral monomeric trimetallic complex C2H5OP(S) (NMeNCHCp'FeCP)2.PdCl2 with the Pd(II) center in a square planar geometry. The structure of 12 is characterized by a six-membered ring with the Pd(II) bonded to two terminal hydrazine units of 7 in a cis disposition. Crystal data of 12: monoclinic, space group P2(1)/c, a = 15.731(3) angstrom, b = 18.695(3) angstrom, c = 11.918(2) angstrom, beta = 98.180(7)degrees, V = 3469.3(10) angstrom3, Z = 4. The structure was solved by direct methods and was refined to R = 0.033.