Cyclopentadienyl complexes with carbonyls

Jiang S, Agoston GE, Chen T, Cabal M-P, Turns E (1995) BF3 Et20-promoted allylation reactions of allyl(cyclopentadienyl)iron(II) dicarbonyl complexes with carbonyl compounds. Organometallics 14 4697 -709... 

A number of molecular mechanics studies of metal-cyclopentadienyl complexes have been reported recently. The systems studied include linear metallocenes (in particular ferrocene), ferrocene derivatives (such as complexes with substituted cy-clopentadienyl ligands, bis(fulvalene)diiron complexes, ferrocenophanes and mixed-ligand complexes with carbonyls and phosphines), and nonlinear cyclopentadienyl complexes 8,153,221 231]. 

The first group 5 cyclopentadienyl complexes with a pendant phosphane ligand were reported very recently by Fryzuk. Ligands 35 and 36 were treated with NbCl3(DME) to give niobium bischelates 207 and 208 in 80% yield (Scheme 35). Carbonylation gave 209 and 210 in 80% yield both were characterized by X-ray structure analyses. Oxidation with PbCL resulted in formation of trichlorides 211 and 212, which can also be obtained from the anionic ligands by treatment with Nb(0)Cl3(THF)2 (Scheme 36). 211 was structurally characterized. ... 

Halides and other salts as well as metal carbonyls sometimes react with cyclopentadiene to afford cyclopentadienyl complexes with concomitant evolution of hydrogen, hydrogen chloride, or other reduction products, such as CjHg. These reactions take place under relatively severe conditions at high temperatures and often under elevated pressures ... 

Two commonly used synthetic methodologies for the synthesis of transition metal complexes with substituted cyclopentadienyl ligands are important. One is based on the functionalization at the ring periphery of Cp or Cp metal complexes and the other consists of the classical reaction of a suitable substituted cyclopentadienyl anion equivalent and a transition metal halide or carbonyl complex. However, a third strategy of creating a specifically substituted cyclopentadienyl ligand from smaller carbon units such as alkylidynes and alkynes within the coordination sphere is emerging and will probably find wider application [22]. 

The chemistry of rhenium(I) is dominated by organometallic compounds which are not covered by this review. Thus, cyclopentadienyl and related compounds, where the organometallic part of the molecule dominate the properties will generally not be considered. Nevertheless, compounds with carbonyl or isocyanide co-ligands will be treated when they can be regarded as constituents of a typical coordination compound or the compounds are of fundamental interest in a radiopharmaceutical context such as the hexakis(isocyanide)rhenium(I) cations. For the same reason a separate section has been included which gives a brief summary of recent attempts to develop synthetic routes to tiicarbonylrhenium(I) complexes for nuclear medical applications. 

This review deals with metal-hydrocarbon complexes under the following headings (1) the nature of the metal-olefin and -acetylene bond (2) olefin complexes (3) acetylene complexes (4) rr-allylic complexes and (5) complexes in which the ligand is not the original olefin or acetylene, but a molecule produced from it during complex formation. ir-Cyclopentadienyl complexes, formed by reaction of cyclopentadiene or its derivatives with metal salts or carbonyls (78, 217), are not discussed in this review, neither are complexes derived from aromatic systems, e.g., benzene, the cyclo-pentadienyl anion, and the cycloheptatrienyl cation (74, 78, 217), and from acetylides (169, 170), which have been reviewed elsewhere. 

Manganese carbonyl, Mn2(CO)io, when treated with tetracyclone at 140-150°, gives an air-sensitive product which on hydrolysis gives the T-cyclopentadienyl complex (LII) 215). Manganese carbonyl does not react with dimcthylacetylene in sunlight, but duroquinone was formed in a similar reaction of the alkyne with [Mn(CO)6] 1 155). Mn(—1) is iso-electronic with Fe(0), and it is suggested that the unstable quinone com-... 

Organosilyl substituted 7)5-cyclopentadienyl complexes may be prepared by two main procedures (a) reactions of silylated cyclopenta-dienes or their alkali metal derivatives, with an appropriate transition metal compound (carbonyl or halide) with formation of ir-bonds (b) metalation of a preformed 7j5-cyclopentadienyl complex, followed by treatment with an organohalosilane. 

A very versatile preparation seems to be the elimination of organotin halides in the reaction of organostannyl-organosilylcyclopentadienes with metal carbonyl halides. This reaction is very selective and only Sn—C bonds are cleaved with formation of 7)5-cyclopentadienyl complexes (7) ... 

CjHjS, Thiophene, tetrahydro-gold complexes, 26 85-87 C4H,NO, 2-Propenamide, 2-methyl-nickel complex, 26 205 C4H1()02, Ethane, 1,2-dimethoxy-solvates of chromium, molybdenum, and tungsten carbonyl cyclopentadienyl complexes, 6 343 tungsten complex, 26 50 ytterbium complex, 26 22 C4H i02.NaC5H5, Ethane, 1,2-dimethoxy-compd. with cyclopentadienylsodium, 26 341... 

Alkynyl complexes with copper, 2, 160 with Cp Re(CO) (alkyne), 5, 916 with dicarbonyl(cyclopentadienyl)hydridoirons, 6, 175 with diiron carbonyls, 6, 232-233 donor-free, with gold(I), 2, 255 with gold(I)... 

Aminoalkenes, oxidative cyclization, 10, 710-711 Aminoalkoxides, on zinc compounds, 2, 371 a-Aminoalkylallenes, cycloisomerizations, 10, 720 a-Aminoalkylcuprates, preparation, 9, 519-520 -Aminoalkylidynes, diiron carbonyl complexes with cyclopentadienyl ligands, 6, 248 Aminoalkynes, hydroamination, 10, 717 a-Aminoallenes, activation by gold, 9, 574 Amino r]5-amides, in Ru and Os half-sandwich rf3-arenes,... 

Binding energy, pentacarbonyliron, 6, 3 Binuclear complexes bis-Cp titanium halides, 4, 522 with Ni-M and Ni-C cr-bonds heterometallic clusters, 8, 115 homometallic clusters, 8, 111 Binuclear dicarbonyl(cyclopentadienyl)hydridoiron complexes, with rand C5 ligands, 6, 178 Binuclear iridium hydrides, characteristics, 7, 410 Binuclear monoindenyl complexes, with Ti(IV), 4, 397 Binuclear nickel(I) carbonyl complexes, characteristics, 8, 13 Binuclear osmium compounds, with hydrocarbon bridges without M-M bonds, 6, 619... 

Bis(amido) phosphine-donor complexes, with Zr(IV), 4, 816 Bis(amido) pyridines, with Zr(IV) and Hf(IV), 4, 790 Bis(aminoalkylidyne) complexes, diiron carbonyl complexes with cyclopentadienyl ligands, 6, 248-251 Bisaminosilylenes, in molybdenum carbonyls, 5, 406 Bis(tj-arc nc) complexes, as metal vapor synthesis milestone, 1, 236... 

Cyclopentadienones, in molybdenum carbonyls, 5, 451 Cyclopentadienyl alkenes, with niobium, 5, 76 Cyclopentadienyl-alkoxo complexes, with Ti(IV), 4, 495 Cyclopentadienyl alkyl complexes, with niobium, 5, 66 Cyclopentadienyl-amido complexes, with Ti(IV), via dehalosilylation, 4, 448... 

Cyclopentadienyl carbonyl complexes, with niobium, 5, 64 Cyclopentadienyl chromium bis(Ti-allyl) complexes, with chromium, 5, 305-306 Cyclopentadienyl chromium carbonyls... 

Deprotonation with aluminum alkys, 9, 272 mononuclear carbonyl iridium complexes, 7, 302 for palladium cyclopentadienyl complexes, 8, 390 in Ru and Os half-sandwich preparations, 6, 569 in silver carbene synthesis, 2, 206 Desulfurization... 

Diiridium(I) complexes, dihydrogen uptake, 7, 289 Diiridium(III) polyhydrides, synthesis and reactivity, 7, 410 Diiron carbonyl complexes with cyclopentadienyl ligands... 

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... 

Manganese carbenes, preparation, 5, 825 Manganese carbonyl complexes with 776-arene complexes, 5, 787 cyclopentadienyl complexes, 5, 783 with hydrocarbon ligands, complexes, 5, 776 synthesis and characteristics, 5, 761 Manganese carbonyl halides, applications and reactivity,... 

Phthalic acid, with trinuclear Os clusters, 6, 743 n-acceptor carbon ligands, in molybdenum carbonyls, 5, 455 Ti-allyl complexes, with molybdenum with cyclopentadienyl-supporting ligands, 5, 544 monomeric complexes, 5, 546 oxide surface binding, 5, 546... 

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