Isonitrile complexes, osmium

Isomer shift data, Fe,S4 clusters, 38 20, 50 Isomorphic substitution, 39 179, 186 p-Isonicotinamide complexes, osmium, 37 307 p-lsonicotinamidepoly(proline) complexes, osmium, 37 307 Isonitrile complexes osmium, 37 245 technetium(I), 41 13-14 technetium(II), 41 31 technetium(IIl), 41 45 Isopolymolybdates, 19 239ff 19 265-280 crystallization from aqueous solution, 19 265-269... 

Isonitriles are isoelectronic with carbon monoxide bnt homoleptic see Homoleptic Compound) isonitrile complexes are more difficnlt to prepare than carbonyl complexes. The reduction of OsXg with ethanol in the presence of methylisonitrile gives OsX2(CNMe)4. The osmium(II) isonitrile complex [Os(CNMe)6] + results from the alkylation of [Os(CN)6]" with MeOS02CF3. More generally, [Os(CNR)6] + can be prepared by reaction of 0s2(02CMe)4Cl2 with alkyl isonitriles. 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

The osmium hydride (CO)ioOs3H2 reacts with isonitriles to give monosubstituted products (CO)io(RNC)Os3H(/2-H), which react further via insertion to give (CO)io(ju-ri -RNCH))(/i-H)Os3. In weak donor solvents, hydride attacks at the carbon whereas strong donor solvents result in hydride attack at nitrogen. The latter reaction results from deprotonation of the hydride complex, followed by reprotonation at nitrogen. 

---