Isocyanide coordination polymers

Finally, the recent synthesis of a series of two-dimensional isocyanide coordination polymers containing rhodium(I) could lead to the development of a new area of metal-containing polymers (50-52). 

Diethynyl-pyridine was reacted with 2 equiv. of (Me2S)AuCl to give a gold alkynyl as an insoluble coordination polymer of unknown structure. This product could be dissolved in organic solvents with cBuNG to afford the bis(isocyanide) complex with an angular structure (Scheme 50).214... 

Boron—nitrogen coordination polymers, with ferrocene, 6, 208 Boron nucleophiles, in conjugate additions asymmetric 1,4-additions, 10, 388 mechanisms, 10, 384 to nitroolehns, 10, 388 to a,/3-unsaturated amides, 10, 386 to a,/3-unsaturated esters, 10, 386 to a,/3-unsaturated ketones, 10, 384 Boron-silicon bonds, addition to alkenes, 10, 760 to alkynes, 10, 758 to allenes, 10, 760 to carbenoids, 10, 766 to 1,3-dienes, 10, 762 to isocyanides, 10, 765... 

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands... 

SYSTEMS AND COORDINATION POLYMERS CONTAINING A TERMINAL ISOCYANIDE LIGAND 48... 

IV. LUMINESCENT ORGANOMETALLIC POLYMETALLIC SYSTEMS AND COORDINATION POLYMERS CONTAINING BRIDGING ISOCYANIDES... 

With these species in hand, coordination polymers were prepared by reaction with isocyanides according to Eq. 7.35 42... 

Another family of coordination polymers of the same type, 47-52, where a diphosphine was used as an assembling unit and tert-butyl isocyanide as the mon-odentate ligand (to be placed at the other vacant site of the tetrahedral about the... 

Analogous materials with cyclopentadienyliron units coordinated to cyclopentadienyl ligands in the main chain, but with shorter G2 spacers, were described in Section 12.06.3.2.2. Polymers with cyclopentadienyl cobalt groups in the main chain have been reported via the treatment of precursor materials that contain cyclopentadienylcobalt groups (e.g., 147) with /-butyl isocyanide followed by... 

They further specify rules governing a catalyst-induced stereoregulation for the incorporation of chiral isocyanide monomers into the polymers during the chain-propagation process (21). The controlling features are a consequence of substituent relative size, and, where it occurs, substituent coordination to nickel (II). This catalyst-induced stereoregulation probably does not apply to the sulfuric acid polymerization of isocyanides. 

Kros et al. reported a polymer-peptide conjugate prepared via nickel-mediated NCA polymerization and a subsequent polymerization of an isocyanide, again using the nickel complex as initiator [111]. The active catalyst is attacked by the more electrophilic isocyanide and the coordinated amine reacts with the isocyanide to yield a carbene-like initiator for the isocyanide polymerization (see Fig. 14). The product can be purified from free residual homopolymers by selective solvent... 

---