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RESEARCH PRODUCT

Mercurated and Palladated Iminophosphoranes. Synthesis and Reactivity

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Reaction of the iminophosphorane Ph3PNC6H4Me-4 (1a) with Hg(OAc)2 and LiCl gives the mercurated iminophosphorane [Hg{C6H3(NPPh3)-2-Me-5}Cl] (2). The latter reacts with NaBr to give [Hg{C6H3(NPPh3)-2-Me-5}Br] (3). 2 reacts with MeC6H4NCO-4 or CX2 (X = O, S) to give [Hg{C6H3(NCNC6H4Me-4‘)-2-Me-5}Cl] (4) or [Hg{C6H3{NCNC6H3(HgCl)-1‘-Me-5‘}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph3PNC6H4R-4 (1b) react with Pd(OAc)2 to give the complexes [Pd{κ2-C,N-C6H4(PPh2NC6H4R-4‘)-2}(μ-OAc)]2 (R = Me (6a), MeO (6b)), in which the palladation takes place at one of the phenyl substituents of the PPh3 group. Complex 6b reacts with NaBr or tBuNC to give [Pd{κ2-C,N-C6H4(PPh2NC6H4OMe-4‘)-2}(μ-Br)]2 (7) or [Pd{κ2-C,N-C6H4(PPh2NC6H4OMe-4‘)-2}(OAc)(CNtBu)] (8), respectively. Complexes 6a,b react with NaClO4 and N,N,N‘,N‘-tetramethylethylenediamine (tmeda), yielding [Pd{κ2-C,N-C6H4(PPh2NC6H4R-4‘)-2}(tmeda)]ClO4 (R = Me (9a), MeO (9b)). The compound Ph3PNC6H4I-2 (1c) adds oxidatively to [Pd2(dba)3]·dba (dba = dibenzylidenea...