Dialkylcyanamides are more reactive substrates toward metal-mediated nucleophilic addition than alkylcyanides†
Abstract
The dialkylcyanamide complexes Q[PtCl3(NCNR2)] (Q = Ph3PCH2Ph, R2 = Me21, Et22, C5H103, C4H8O 4; Q = NMe4, R2 = Me25; Q = NEt4, R2 = Me26) were synthesized either by dissolving Q2[Pt2(μ-Cl)2Cl4] in neat NCNR2 (1–4) or by substitution of a NCNR2 C(H)Ph}] (Q = Ph3PCH2Ph, 13; Me4N, 14; Et4N, 15) and the corresponding dialkylureas H2NC(
O)NR2. The competitive reactivity study of the nucleophilic addition of HON(CH2Ph)2 to (Ph3PCH2Ph)[PtCl3(NCR′)] (R′ = Ph, NR2, CH2Ph) indicated that the reactivity of the coordinated NCNR2 is comparable to NCPh, while NCCH2Ph appeared to be much less reactive than the former two