Syntheses and structures of the complexes cis-[M(C6F5)(2)(NX)] (M=Pd, Pt; NX=2-iodoaniline, 2-benzoylpyridine) containing N X acting as a didentate chelating ligand and displaying I->M or O->M interactions

Complexes cis-[M(C6F5)(2)(THF)(2)] (M = Pd, Pt) are weak Lewis acids and react with the halocarbon ligand 2-iodoaniline (R-I) yielding the corresponding cis-[M(C6F5)(2)(R-I)] [M = Pd (1), Pt(2)]. Tn these complexes a (C-)I-M bond is present. The use of other 2-haloanilines (halogen = F, Cl, Pr) does not yield the analogous complexes because of the lesser nucleophilic character of the halogen involved. The presence of the (C-)I-Pt bond in 2 has been confirmed by an X-ray structure determination, which also reveals an N-H M hydrogen bond between two neutral molecules. Complex 2 crystallizes in the space group P (1) over bar: Z = 4; a = 11.797(4) Angstrom; b = 13.735(4) Angstrom; c = 14.107(4) Angstrom; alpha = 97.24(2)degrees; beta = 90.91(2)degrees; gamma = 99.44(2)degrees; V = 2235(2) Angstrom(3). Similarly, complexes cis-[M(C(6)X(5))(2)(THF)(2)] (M = Pd, Pt; X = F, Cl) react with the ligand 2-benzoylpyridine {R-C(O)Ph}, in which the oxygen atom of the ketonic group can behave as a nucleophilic center, yielding the complexes cis-[M(C(6)X(5))(2){R-C(O)Ph}] [M = Pd, X = F (3); M = Pt, X = F (4), Cl (5)]. Complex 3 crystallizes in the space group C2/c: Z = 16; a = 26.284(3) Angstrom; b = 10.623(1) Angstrom; c = 31.423(4) Angstrom; beta = 93.15(1)degrees; V = 8760(2) Angstrom(3). The I-M or O-M bonds in complexes 1-5 are weak and can be easily broken by the addition of neutral (CO, PPh(3), and CH3CN) or anionic (Br-) ligands.