Chlorobis complexes

Several trialkoxy(2-butenyl)zirconium(IV)6,7i 18 and 2-butenylbis(cyclopentadienyl)zirco-nium(IV)18,19 124 complexes have been investigated with respect to the diastereoselectivity on addition to aldehydes. Chlorobis(cyclopentadienyl)-(3-tributylstannyl-2-propenyl)zirconium(IV), prepared by hydrozirconation of tributyl-(l,2-propadienyl)tin, accomplishes the (E)-selective, Wittig-like 1,2-propenylidenation of aldehydes and methyl ketones125. 

Uson, R., Laguna, A. and Cuenca, T. (1980) Chlorobis (polyfluorophenyl) thallium(III) complexes and their reactions with gold(l) and tin(ll) compounds. Journal of OrganometaUic Chemistry, 194(3), 271-275. 

Uson, R., Laguna, A., Laguna, M., Uson, A. and Gimeno, M.C. (1988) Reactions of pentafluorophenyl(ylide)silver(I) or -gold (I) complexes with chlorobis... 

The reaction of racemic Sb-chiral l-phenyl-2-trimethylsilylstibindole with the optically active ortho-palladated benzylamine derivative, di-p-chlorobis (S)-2-[l-dimethylamino)ethyl]phenyl-C,N dipalladium, leads to diastereomeric complexes which were used for the separation of the enantiomers of the stibindoles.65 The molecular structures of the diastereomeric palladium complexes are depicted in Fig. 4. 

In the United States PCB preparations are marketed under the trade name Aroclor and consist of complex mixtures of chlorobi-phenyls. Table I gives the chlorobiphenyl composition of some... 

The complexes of thiomorpholin-3-one, (CuLI) and [Cu2L4C12] are diamagnetic compounds probably containing Cu—S co-ordination.602 Chlorobis(2-thiouracil)-copper(i),DMF, formed from copper(n) chloride and thiouracil, contains almost trigonal-planar Cu1 with S2C1 co-ordination.653... 

Reaction of chlorobis(methylene)phosphorane 55 with K[(i73-C3H5)Fe(CO)3] in a mixture of THF and toluene gives the metallobis(meth-ylene)phosphorane 56 and the bis(methylene)propenylphosphorane 57 as major products. The dihydrophosphole complex 58 is obtained as a minor product (<10% yield) (Scheme 13).40 In contrast, treatment of 55 with K[Fe(CO)2Cp] gives rise to the formation of the metallobis(methylene) phosphorane 59 (39% yield) and the phosphaferrocene 60 (34-72% yield, dependent upon the reaction time). The phosphole ligand of 60 is con-... 

Complexes of racemic ( )-l-phenyl-2-trimethylsilylstibindole 28 <1990AGE771> with optically active di-fi-chlorobis (A )-2-[l-(dimethylamino)-ethyl]phenyl-C ,At dipalladium(ll) 29 were separated by chromatography on silica gel using dichloromethane/hexane/diethyl ether (10 10 1) <2000CC191>. 

Resolution of the racemic 7-/i-tolyldinaphtho[2,l-4 T,2 -optically active palladium complexes (with O.Sequiv of dimeric optically active di-p.-chlorobis (4)-2-[T(dimethylamino)-ethyl]phenyl-(7,M dipalladium(n)) 29 is a rare example of a reaction giving a product with CN 4 (Equation 6). The diastereomeric mixture thus produced could not be separated by fractional recrystallization from a variety of solvents or by column chromatography, because the optically active 7-A-tolyldinaphtho[2,l-4 l, 2 -palladium complex 48. Also the complex prepared from enantiomerically pure R-(-)-stibole 16 racemizes due to fluxionality (NMR estimated at elevated temperatures) <2001TL441, 2003YZ577>. 

Chlorobis[l,3-bis(diphenylpho phine)propane]rhodium, Rh(dppp),Cl (1). The complex is prepared by heating COClRh P(Cf,Hs),], with the phosphine in xylene. ... 

Di-p.-chlorobis(l,5-hexadiene)dirhodium, [Rht l( 1,5-CfiH )],(l). The complex is prepared by reaction of the diene with RhCl., in aqueous C,H,OH. ... 

METHYLENATION Alkyidimesitylboranes. p,-Chlorobis(cyclopentadienyl)(dimethyl-aluminum)-p.-methylene-titanium. Methylene bromide-Zinc-Titanium(IV) chloride. Organomolybdenum reagents. Titanocene methylene-Zn halide complex. N,N,P-Tri-methyl-P-phenylphosphinothioic amide. Trimethylstannylmethyllithium. 

REDUCTION, REAGENTS Bis(triphenyl-phosphine)copper tetrahydroborate. Borane-Pyridine. Calcium-Methylamine/ ethylenediaminc. Chlorobis(cyclopenta-dienyl)tetrahydroboratozirconium(IV). Chromium(II)-Amine complexes. Copper(0)-lsonitrile complexes. 2,2-Dihydroxy-l, 1-binaphthyl-Lithium aluminum hydride. Di-iododimethylsilane. Diisobutyl-aluminum 2,6-di-/-butylphenoxide. Diisobutyl aluminum hydride. Dimethyl sulfide-Trifluoroacetic anhydride. Disodium tetracarbonylferrate. Lithium-Ammonia. Lithium-Ethylenediamine. Lithium bronze. Lithium aluminum hydride. Lithium triethylborohydride. Potassium-Graphite. 1,3-Propanedithiol. Pyridine-Sulfur trioxide complex. 

Chlorobis(cyclopentadienyl)tetnihydrobor8tozirconiuni(IV), Cp2Zr(CI)BH4. Mol. wt. 271.70. An early preparation has been reported without details. A convenient preparation involves reaction of Cp2Zr(H)Cl and BHi-S(CHj)2 yield 70-80%. Reduction of carbonyl groups Aldehydes and ketones are reduced by this complex in high yield esters, carboxylic acids, nitriles, and nitro compounds are reduced very slowly. The reagent thus resembles NaBH4, but can be used for reductions in benzene. 

The stretched porphycenes have shown some promise as ligands for the com-plexation of transition metal cations. For instance, when [22]tetradehydroporphyrin-(2.2.2.2) 4.115 is treated with di-p-chlorobis[dicarbonylrhodium(I)] in dichloro-methane using potassium carbonate as base, a bis[Rh(CO)2] complex is formed. ... 

F,CIOiPtSC H, Platinum(II), chlorobis-(triethylphosphine)(trifluoromethane-sulfonato)-, cis-, 26 126 FiK2MnOjS, Manganate(III), trifluorosul-fato-, dipotassium, 27 312 FiMhOkSC, Manganese(I), pentacarbonyl-(trifluoromethanesulfonato)-, 26 114 F,02CH, Acetic acid, trifluoro-, tungsten complex, 26 222... 

Furthermore, a chlorobis(allyl)- and a dichloromono(allyl)neodymium complex could be prepared by the comproportionation reactions formulated in eqs. (3) and (4) [39]. 

Cyclopropylcyclopropanes have been obtained in several ways from nickel complexes that have been preformed by reaction with 3,3-dimethylcyclopropene. Their formation occurs as a side reaction of cyclodimerization. Complex 12 is formed in 49% yield from trans-A -chlorobis(trimethylphosphane)nickel (11) and excess 3,3-dimethylcyclopropene in the presence of magnesium. ... 

Conversion of norbornadiene to nortricyclenes can also be achieved with organomercurials. This reaction proceeds via transmetalation to form a c-bonded organopalladium system which inserts norbornadiene. Thus an enrfo-cw-addition is observed. Conversions of this type were observed in the phenylation of dichloro(t -norbornadiene)palladium either with diphenyl-mercury or, more conveniently, with sodium tetraphenylborate to give di-/r-chlorobis(2 5,6-t -c ffo-3-phenylbicyclo[2.2.1]hept-e /o-2-yl)palladium (30) via cis addition.By contrast, the analogous platinum complex did not give a phenylation product. The palladium complex 30 underwent reversible ring closure to a nortricyclenyl complex 31 with pyridine. ... 

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