Octakis

Perfluorodecalin is transformed to octakis(phenylthio)naphthalene by phenyl thiolate in dipol ar aprotic solvents The crucial first step of this reaction may involve an elimination of the tertiary fluorine atoms, which would lead to a symmetric perfluorobicyclic olefin as an intermediate [65] (equation 58). 

Zinc, chlorohexadecakis(pheny thio)octakis-, 1,137 Zinc, dialkyl-oxidation, 2, 342 Zinc, dicyano-... 

The first pyrrolylphosphazenes were apparently prepared by McBee and coworkers in 1960, and although the work was never documented in the chemical literature, hexakis-(pyrrolyl)cyclotriphosphazene (1) and octakis-(pyrrolyl)cyclotetraphosphazene were described in a Technical Report of the Defense Technical Information Center.19 Compound 1 was reported to be produced in 26% yield from the interaction of hexachlorocyclotriphosphazene [(NPC 2)3] with excess potassium pyrrolide in refluxing benzene over a 24 hour period. Lithium pyrrolide and pyrrolyl magnesium bromide were found to be unsatisfactory reagents for the preparation of 1. 

Octakis(trifluorophosphine)dirhodium See Octakis(trifluorophosphine)dirhodium Acetylenic esters See other acetylenic compounds... 

A novel tetraazaporphyrinato (TAP) and phthalocyaninato mixed het-eroleptic rare-earth compound, LnPc (TAP) with photochromic and electrochromic features has been readily synthesized by a one-pot reaction using Eu(acac)3-wH20, metal-free phthalocyanine H2Pc (Pc = 2,3,9,10,16,17,23,24-octakis(decyloxy)phthalo-... 

Thermolysis of compound 47 in the presence of benzophenone or naphthalene at 200-220 °C provides two products, 2,2,4,4,5,5-hexakis(2,6-diethylphenyl)pentastanna-[l,l,l]propellane, 49, and octakis(2,6-diethylphenyl)octastannacubane89, 50, as well as traces of R SnSnRj. 

Nitrogen substituted porphyrazines were the second type of heteroatom-deriva-tized pz macrocycle reported and were prepared from the readily derivatized diami-nomalconitrilc (DAMN) (7). Octakis(dimethylamino)porphyrazines are extremely electron-rich systems and have been used to prepare charge-transfer complexes with Cgo, as well as to peripherally chelate metals or convert to crown appended systems (38, 39). The unsymmetrical dimethylaminoporphyrazine analogues have also been reported (29), as well as the first example of the desymmetrized seco-pz from the dimethylaminoporphyrazine (8, 40). The nitrogen substituted porphyrazines are discussed in Section V. 

M[pz(A4)] A = S2ML2. The octakis(.V-R)porphyra/,ines reported by Schramm and Hoffman (2), M[pz(S-R)8 (M = Ni, Cu), (60), can be converted to the octathiolate M[pz(S )g] (Scheme 11) via reductive cleavage of the sulfur-carbon bond when R = benzyl (Bn), and this tetra-bis(dithiolate) can then be peripherally capped with metal-ligand systems to yield peripherally tetrametalated star porphyrazines. The benzyl dinitrile 57 can be macrocyclized around magnesium butoxide to form [Mg[pz(S-Bn)8] (58) (35-40%), which can then be demetalated with trifluoroacetic acid to form 59 (90%), which is subsequently remetalated with nickel or copper acetate to form 60a (95%) and 60b (70%) (Scheme 11) (3, 23, 24). Deprotection of 60a or 60b with sodium in ammonia yields the Ni or Cu tetra-enedithiolates, 61a or 61b to which addition of di-ferf-butyl or n-butyl tin dinitrate produces the peripherally metalated star porphyrazines 62a (37%), 62b (80%), and 62c (41%). 

Octakis(trifluorophosphine)dirhodium, Acetylenic esters, 4387 Phenylacetylene, 2912... 

A number of methyl substituted PyO have been tried as ligands for coordination with the lanthanides. Depending on the position of the substituent, these ligands impart different degrees of steric strain for the formation of complexes. Since substituents in the 4 or 3 position do not introduce substantial steric hindrance to coordination, Harrison and Watson (160) could synthesize octakis-4-MePyO complexes. Subsequently, Koppikar and Soundararajan (161) could also synthesize octakis-3-MePyO complexes with lanthanide perchlorates. Complexes of 4-MePyO (162, 163) and 3-MePyO (164, 165) with lanthanide iodides and bromides also have a L M of 8 1. 

Fig. 46.3 FT-IR spectrum of [2,3,7,8,12,13,17,18-Octakis(3-phenyl-2-propenethio)-porphyrazi-nato] Mg(II)...

VII = Heptakis (2,6-di-0-methyl-3-0-pentyl)--P--cyclodextrin + Octakis (2,6-di--0-methyl-3-0-trifluoroacetyl)-y-cyclodextrin... 

VIII = Octakis (2,3-di-0-acetyl-6-0-tert-butyldimethylsilyl)--y--cyclodextrin... 

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