88657-08-3Relevant academic research and scientific papers
Functionalized isocyanides as ligands. Synthesis of 2-(chloromethyl)- and 2-(iodomethyl)phenyl isocyanides and their transition-metal complexes
Michelin, Rino A.,Facchin, Giacomo,Uguagliati, Paolo
, p. 961 - 969 (2008/10/08)
Isocyanides of the general structure 2-(XCH2)C6H4NC (X = Cl, 2-(chloromethyl)phenyl isocyanide (CN'down curve sign'CH2Cl); X = I, 2-(iodomethyl)phenyl isocyanide (CN'down curve sign'CH2I)) have been prepared through a four-step synthesis starting from 2-(chloromethyl)benzoyl chloride and proceeding through successive formation of the corresponding azide, isocyanate, and formamide. The iodo isocyanide was obtained from the parent chloride by halide exchange with NaI in acetone. Such ligands, which contain both isocyanide and alkyl halide (CH2X) functions, can act as monofunctional or bifunctional ligands. Reactions involving the isocyanide function lead to mononuclear complexes of the type M(CO)5(CN'down curve sign'CH2X) (M = Cr, W; X = Cl, I), cis-MCl2(PR3)(CN'down curve sign'CH2Cl) (M = Pd, Pt; PR3 = PPh3, PMePh2, PMe2Ph), and cis-MCl2(CN'down curve sign'CH2Cl)2. Reaction of CN'down curve sign'CH2I with [Pt(PMePh2)Cl2]2 yields a mixture of PtClI(PMePh2)(CN'down curve sign'CH2Cl) (major product), PtCl2(PMePh2)(CN'down curve sign'CH2Cl), and PtI2(PMePh2)(CN'down curve sign'CH2I). Insertion reaction of CN'down curve sign'CH2Cl into the Pt-H bond in trans-PtHCl(PPh3)2 gives the formimidoyl complex trans-PtCl(PPh3)2(CH=N'down curve sign'CH2Cl). In some of these mononuclear isocyanide derivatives the dangling CH2I function shows some typical reactions of halide displacement by aromatic amines or metal carbonyl anions, leading to new organometallic o-aminobenzyl isocyanide complexes of the type M(CO)5(CN'down curve sign'CH2NH-p-C6H4Me) (M = Cr, W) and homo- and heterobinuclear derivatives of the types M(CO)5(CN'down curve sign'CH2)M′Cp(CO)3 (M = Cr, M′ = Mo; M = W, M′ = Mo; M = M′ = W) and W(CO)5(CN'down curve sign'CH2)Mn(CO)5. The CH2I function in M(CO)5(CN'down curve sign'CH2I) (M = Cr, W) also undergoes oxidative addition to Pd(0) and Pt(0) complexes, affording the binuclear complexes M(CO)5(CN'down curve sign'CH2)-trans-M′I(PPh3)2 (M = Cr, W, M′ = Pt; M = Cr, M′ = Pd). Oxidative addition of the uncoordinated CN'down curve sign'CH2I to Pt(PPh3)2(C2H4) leads instead to the dimeric Pt(II) derivative (Chemical Equation Presented).
