R/X exchange reactions in cis-[M(R){P(X)(NMeCH)}] (M = Pd, Pt; R = aryl, alkyl; X = Cl, Br) were achieved for the first time to give cis-[M(X){P(R)(NMeCH)}]. DFT calculations suggested that the exchange reaction proceeds via a phosphenium intermediate.
Reaction of dialkyl-or diaryl-platinum complexes PtR 2 (cod) (cod = h 2 , h 2 -1,5-cyclooctadiene, R = Me, p-tol) with diamino-substituted phosphorus ligands P(NMeCH 2 ) 2 (R 0 ) (R 0 = OMe, NEt 2 ) produced neutral complexes, cis-[Pt(R) 2 {P(NMeCH 2 ) 2 (R 0 )} 2 ]. On the other hand, reaction of dihalogeno platinum complex PtX 2 (cod) (X = Cl, I) with P(NMe-CH 2 ) 2 (OMe) yielded a cationic complex [PtX{P(NMeCH 2 ) 2 (OMe)} 3 ]X. A platinum complex having both methyl and halogeno ligands, PtMeX(cod), reacted with P(NMeCH 2 ) 2 (OMe) to give a cationic methyl complex [PtMe{P(NMeCH 2 ) 2 (OMe)} 3 ]X, by contrast, it reacted with P(NMeCH 2 ) 2 (NEt 2 ) to yield a neutral methyl complex [PtMeX{P(NMeCH 2 ) 2 (NEt 2 )} 2 ]. Reaction of [PtMe{P(NMeCH 2 ) 2 (OMe)} 3 ]X with BF 3 ÁOEt 2 and then NaBPh 4 afforded [PtX{P(NMeCH 2 ) 2 (OMe)} 3 ]BPh 4 , showing preferential Me group abstraction on the Pt center rather than the OMe abstraction on the phosphorus atom, followed by the coordination of X to the Pt center. All new complexes were fully characterized using 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR measurements and elemental analyses. In addition, structures of several complexes were determined by single crystal X-ray diffraction studies.
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