2,2-bis >75-cyclopentadienyl

The full ab-initio molecular dynamics simulation revealed the insertion of ethylene into the Zr-C bond, leading to propyl formation. The dynamics simulations showed that this first step in ethylene polymerisation is extremely fast. Figure 2 shows the distance between the carbon atoms in ethylene and between an ethylene carbon and the methyl carbon, from which it follows that the insertion time is only about 170 fs. This observation suggests the absence of any significant barrier of activation at this stage of the polymerisation process, and for this catalyst. The absence or very small value of a barrier for insertion of ethylene into a bis-cyclopentadienyl titanocene or zirconocene has also been confirmed by static quantum simulations reported independently... 

Further simulations have been performed. In contrast to what was observed for bis-cyclopentadienyl metallocenes, mono-cyclopentadienyl systems did reveal a significant barrier to insertion [lOj. However, for all these systems it turned out that insertion only proceeded after the formation of a relatively stable agostic interaction, an observation that clearly supports the Brookhart-Green mechanism. 

Examples of photothermoplasts include polyacrylates, polyacrylamides, polystyrenes, polycarbonates, and their copolymers (169). An especially well-re searched photothermoplast is poly(methyl methacrylate) (PMMA), which is blended with methyl methacrylate (MMA) or styrene as a monomer, and titanium-bis(cyclopentadienyl) as a photoinitiator (170). 

Fig. 4. Representative structures for compounds of molybdenum(IV) (a) bis(diaIkyldithiocarbamato)oxomolybdenum(IV), MoO(S2CNR2)2, where R = alkyl (b) / Jtetracyanodioxomolybdenum(IV), Mo02(CN) (c) M03SJ3 (d) Mo3S4(SCH2CH2 )1 (e) Mo304(H20)g" (f) the Mo M S thiocubane core stmcture (g) bis(cyclopentadienyl)dichloromolybdenum(IV), CP2M0CI2, where Cp = cyclopentadienyl.

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Lead (bis-cyclopentadienyl) [1294-74-2] M 337.4. Purified by vacuum sublimation. Handled and stored under N2. 

Mercury(II) bis(cyclopentadienyl) [18263-08-6] M 330.8. Purified by low-temp recrystn from Et20. 

Nickelocene [bis-(cyclopentadienyl)nickel II] [1271-28-9] M 188.9, m 173-174 (under N2). Dissolve in Et20, filter and evaporate in a vacuum. Purify rapidly by recrystn from pet ether using a solid C02-Me2C0 bath, m 171-173°(in an evacuated tube). Also purified by vacuum sublimation. [J Am Chem Soc 76 1970 954 J Inorg Nud Chem 2 95, 110 7956.]... 

Stannous bis-cyclopentadienyl [26078-96-6] M 248.9. Purified by vacuum sublimation, and stored under dry N2. The related thallium and indium compounds are similarly prepared. 

Zirconocene dichloride (bis[cyclopentadienyl]zirconium dichloride) [1291-32-3] M 292.3, m 242-245 , 248 . Purified by recrystn from CHCI3 or xylene, and dried in vacuum. H NMR (CDCI3) 8 6.52 from MeaSi. Store in the dark under N2 as it is moisture sensitive. [IR, NMR, MS Aust J Chem 18 173 7965 method of J Am Chem Soc 81 1364 7959 and references in the previous entry.]... 

Sulfur imides with a single NR functionality, S5NR (6.12), SeNR (6.13) (R = Oct), " SgNH (6.14), ° and S9NH (6.15) ° are obtained by a methodology similar to that which has been used for the preparation of unstable sulfur allotropes, e.g., S9 and Sio. Eor example, the metathesis reaction between the bis(cyclopentadienyl)titanium complexes 6.8-6.10 and the appropriate dichlorosulfane yields 6.14 and 6.15 (Eq. 6.4). °... 

Amongst these are bis(cyclopentadienyl) and bis(y3-diketonate) derivatives, some of which are undergoing clinical trials, in the hope that they will provide more extensive application than cisplatin (pp. 1163-4). 

Bis(cyclopentadienyl)zirconium 1,3-alkadiene complexes19-20 show interesting stepwise double insertion reactions to carbonyl compounds, exploration with respect to their stereochemical features has only just begun21-23. 

A convenient method for the preparation of 2-alkenylbis(cyclopentadienyl)zirconium(IV) alkoxides and -trialkylsilyloxides is the reductive metalation of the appropriate alkyl or silyl ethers by means of in situ generated bis(cyclopentadienyl)zirconium(II) 124. 

Bis-[athyl-cydopcntadienyl-eisen)-methyl- 589 Bis-[cyclopentadienyl-eisen]-mcthyl- 589... 

New kinds of living polymer systems result from the reactions of transition metals with cyclic, strained olefins 16). These polymerizations proceed through the intermediacy of metal carbenes and are exemplified by the polymerization of norbomene initiated by bis(cyclopentadienyl)-titane-cyclobutane described recently by Grubbs17>. 

Reaction of an alkyl (usually trimethyl) of Group-IIIb element (Al, Ga, In) with a hydride of a Group-Vb element (P, As, Sb) at 600-800°C and 1 atm. [4i][42] p. doping obtained from addition of diethyl zinc or bis(cyclopentadienyl) magnesium. 

MOCVD of Zirconia. Yttria-stabilized zirconia is also deposited by MOCVD.Deposition can be accomplished by the codecomposition of the tetramethyl heptadiones of zirconium and yttrium, Zr(CjjHj902)3 and Y(CjjHj902)3, at 735°C. Deposition is also achieved by the decomposition of the trifluoro-acetylacetonates in a helium atmosphere above 300°C.P 1 Other potential MOCVD precursors are bis(cyclopentadienyl)zirconium dichloride, (C5H5)2ZrCl2, and zirconium (IV) trifluoroacetylacetonate,... 

The molar ratio of the III compound to the V compound is typically l/lO.t ] To obtain the desired semiconductor properties, dopants are added such as zinc (from diethyl zinc) or magnesium (from bis(cyclopentadienyl) magnesium) for p doping, and silicon (from silane) or selenium (from hydrogen selenide) for n doping. 

Also known are the bis(cyclopentadienyl) zirconium formamidinates Cp2ZrCl[HN(NR)2] and CpzZrMelHNfNRlzl (R = Cy, Ph). The latter could be... 

Of the 24 lines expected for coupling between V (I =7/2) and two equivalent C (I = V ) nuclei, 18 were resolved in the epr spectrum of VO(S CNEt2)2, showing that the C(2s) orbital can also participate in transannular interactions (61). [Cp2V(S2CNEt2)BF4] and dithiophos-phate have been used in an extension of studies on the C4V oxovana-dium(IV) chelates to yield C2V bis(cyclopentadienyl) complexes. 

Conjugated dienes can add hydrogen by 1,2 or 1,4 addition. Selective 1,4 addition can be achieved by hydrogenation in the presence of carbon monoxide, with bis(cyclopentadienyl)chromium as catalyst. With allenes catalytic hydrogenation usually reduces both double bonds. 

Bis(cyclopentadienyl) complexes are central to the organometallic chemistry of the early transition metals and feature in applications such as alkene polymerization chemistry. Parallels can be drawn between a porphyrin ligand and two cyclopentadienyl ligands, in that they both contribute a 2— formal charge and exert a considerable steric influence on other ligands in the same molecule. Several of the metalloporphyrin complexes discussed below have bis(cyclopentadienyl) counterparts, and authors in some ca.ses have drawn quite detailed comparisons, although these discussions will not be repeated here. 

Finally, the cyclopentadienyl radical, C5H5, was obtained by vacuum pyrolysis (970°C, 10 Torr) of bis(cyclopentadienyl)nickel (18) and it was frozen into an argon matrix at 12 K (Nefedov, 1991a,b Korolev and... 

The ability to control the polymer from the design of the catalyst, coupled with high catalytic efficiency has led to an explosion of commercial and academic interest in these catalysts. Exxon started up a 30 million lb/5rr ethylene copol3rmer demonstration plant in 1991 using a bis-cyclopentadienyl zirconium catalyst of structure 1. The Dow Chemical Company (Dow) began operating a 125 million Ib/yr ethylene/l-octene copolymer plant in 1993 and has since expanded production capacity to 375 million Ib/yr. This paper will focus on the structure / property relationships of the catalysts used by Dow to produce single-site ethylene a-olefin copolymers. 

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