Isocyanide complexes reaction with azides

A number of studies have been reported concerning azide-isocyanide condensations to give tetrazoles. Early work by Beck and co-workers 18, 19) describes the addition of various isocyanides to metal azido species [Au(N3)4]", [Au(N3)2]", Au(PPh3)N3, and M(PPh3)2(N3)2, M = Pd, Pt, Hg. The products are carbon-bonded tetrazolato-metal complexes. It is not known whether metal isocyanide complexes are intermediates in these reactions. More recently inverse reactions with azide ion addition to metal isocyanide complexes were carried out, with similar results. From... 

Beck and Fehlhammer (18, 19) describe reactions of several metal azide complexes, including Au(N3)4, with isocyanides which yielded a tetrakis-(tetrazolato)aurate(I) species. The formation of Au(PPh3)C(OCH3)=N-p-... 

We first reported that the 16-electron rhodium fragment [Tp Rh(CNR)] where CNR = neopentyl isocyanide could activate hydrocarbon C-H bonds by irradiation of the carbodiimide precursor in benzene [1]. 366 nm irradiation of the yellow complex 1 led to the colorless phenyl hydride product in good yield. The quantum yield was determined to be 1.0 0.3, which is higher than for many other organ-ometallic photoprecursors [2-6]. Compotmd 1 is readily prepared by the reaction of phenyl azide with the Tp Rh(CNR)2. 

The reaction of (CH3C5H4)3U THF with organic azides and with organic isocyanides yields uranium imido (equation (22.17)) and isocyanato (equation (22.18)) complexes [32] ... 

The azide ligands in the complexes [M(N3)aL2] (M = Pd or Pt L = tertiary phosphine) can act as 1,3-dipoles and form a number of [2 + 3] cycloaddition products with organic nitriles, isocyanides, thiocyanates, isothiocyanates, carbon disulphide, and dimethyl acetylenedicarboxylate. Some of the reactions are summarized in Scheme 2. The rate of reaction of cis-[Pt(N3)2L2] with pam-substituted benzonitriles RCeHiCN increases in the... 

With substrates featuring a more energetic, multiply unsaturated polarized bonding scheme, like carbodiimides or isocyanides, a [2+2] cycloaddition reaction to the C=Y bond subsequent to the preliminary nucleophilic attack of the benzyl ligand could be observed [68] (Scheme 17). The same cycloaddition was also observed with those substrates and the corresponding iodinated yttrium complex, which also reacted with tert-butyl phosphaalkyne [67]. However, no subsequent [2+2] cycloaddition was observed with pivalonitrile or adamantly azide on the benzylated complex. 

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