Phenylbis

Phenylstibine [58266-50-5] C H Sb, has been obtained by the reduction of phenyldiio do stihine [68972-61-2] CgH3l2Sb, (73) or phenyldichlorostibine [5035-52-9] 031130.2, (74) with lithium borohydride. It has also been prepared by the hydrolysis or methanolysis of phenylbis(trimethylsilyl)stibine [82363-95-9] C22H23Si2Sb (75). Diphenylstibine [5865-81-6] C22H22Sb, can be prepared by the interaction of diphenylchlorostibine [2629-47-2] C22H2QClSb, with either Hthium borohydride (76) or lithium aluminum hydride (77). It is also formed by hydrolysis or methanolysis of diphenyl (trimethylsilyl)stibine [69561-88-2] C H SbSi (75). Dimesitylstibine [121810-02-4] h.3.s been obtained by the protonation of lithium dimesityl stibide with trimethyl ammonium chloride (78). The x-ray crystal stmcture of this secondary stibine has also been reported. 

Many types of phosphorus-phosphorus bonds are known, but it is rare to find such bonds in hexacoordinated phosphorus compounds (with the exception of 57). Cavell reported in 1998 the reaction of PCI5 with phenylbis(o-(trimethyl-siloxy)phenyl)phosphane, yielding the corresponding bischelate 61 in decent yield (52%) [99]. The octahedral nature of the central phosphorus atom was unambiguously determined by X-ray structural analysis. Two short axial bonds (2.202 A) lie perpendicular to the pseudo-octahedral equatorial plane. 

Examples of w-allylnickel-X compounds (X = anionic ligand) other than 77-allylnickel halides which have been used in combination with (alkyl)aluminum halides as olefin oligomerization catalysts are 7r-allyl-nickel acetylacetonate (11) (Section III), 7r-allylnickel aziridide (4, 56), and bis(7r-allyl)nickel (6) (59). In addition to ir-allylnickel halides, organo-nickel halides such as tritylnickel chloride (60, 61) and pentafluoro-phenylbis(triphenylphosphine)nickel bromide (62), or hydridonickel halides, e.g., trans-hydridobis(triisopropylphosphine)nickel chloride (12) (Section III), give active catalysts after activation with aluminum halides... 

The heterocyclic acylphosphines (52) and (53) have been prepared by the reaction of phenylbis(trimethylsilyl)phosphine with the acid chlorides derived from phthalic and diphenic acids. The reaction of 2,3-dichloromaleic anhydride or thioanhydride with phenylbis(trimethylsilyl)phosphine gives derivatives of the 1,4-dihydro-p-diphosphorin system (54).45... 

CIO ) (octahedral).Phenylbis(dimethylamino)phosphine oxide forms the complexes, [FelPhPfOlfNMe ) (X = CIO or... 

I, I-B1s(trifluoroacetoxy)iodo]benzene Iodine, phenylbis(trifluoroacetato-O-)- (9) (2712-78-9)... 

Schlenk was the one who first took triphenylmethyl-type radicals to the monomeric extreme and thus produced the final evidence for the existence of free radicals. The first example in this direction was phenylbis(biphenylyl)-methyl (11), which was isolated as white crystals from operations carried out in the apparatus described by Schmidlin. " Upon dissolution of 11 in benzene, a red color developed, and cryoscopic studies revealed that the monomeric phenylbis(biphenylyl)methyl constituted 80% of the equilibrium mixture. Trisbiphenylylmethyl (12) was even more extreme it formed black crystals and was a 100% monomeric free radical in an almost black solution. Finally, Schlenk et al. established the connection between the conducting solutions of triphenylhalomethanes and the free radical triphenylmethyl by showing that the cathodic reduction of triphenylbromomethane in liquid SO2 gave rise to triphenylmethyl. These findings were considered the definitive evidence for the free radical hypothesis, and Schlenck was nominated for the Nobel Prize in 1918 and several times afterwards for this achievement, amongst others (Table 2). 

Treatment of 2,2,6-trimethylcyclohexanone with lithium di-isopropylamide (LDA) followed by phenyltriflimide (Af-phenylbis (trifluoromethanesulphonimide) gave the corresponding triflate [24]. The... 

Two types of three-coordinate selenium(II) complexes, isolated as the triselenocyanate and the triselenourea salts, and which have essentially similar structures, have been identified.66 Several three-coordinate tellurium(II) complexes have also been obtained67 when one of the ligands has a very strong trans effect, for example a phenyl group, as in phenylbis(thiourea)tellurium(II) chloride.68... 

HYDROQUINONE,RESORCINOL, AND CATECHOL] (Vol 13) Phenylbis(tnmethylsilyl)stibme [82363-95-9]... 

Hexafluoro-,V-phenylisobutammidyl fluoride (1) reacts with potassium hydroxide to give A/-phenylbis(trifluoromcthyl)keteniininc (2).92 95... 

Methylbis(methylthio)sulfonium hexachloroantimonate ([CH3S(SCH3)2][SbCl6]) was isolated from the reaction mixture at -40°C by the oxidation of nonpoly -merizable dimethyl disulfide [86], This result suggests that the phenylbis(phenyl-thio)sulfonium cation is produced by the oxidation of diphenyl disulfide in the acidic reaction mixture [87-89], This cation acts as the active species for the polymerization and electrophilically reacts with the / -position of the benzene ring to yield PPS [90],... 

The binaphthohydroquinone skeleton is accessible by a double benzannulation of a bi-phenylbis(carbene) complex using two equivalents of alkyne. Application of one alkyne equivalent affords the mono-benzannulated product the second benzannulation step proceeds with distinctly lower yield [68a]. A complementary approach to biaryls is based on 1,3-dialkynes (for example, 64) which undergo a stepwise benzannulation sequence (for example, yielding 65 and 66) (Scheme 26) [68c]. A one-step protocol starting from the ethylene-bridged bis-carbene complex 67 affords the conformationally less flexible biaryl 68, albeit in only moderate yield. 

Mass spectra of pentaphenyl-, methyl bis-2,2 -biphenylene and phenylbis-2,2 -biphenylene antimonys have been investigated by Hellwinkel et al.51. Mossbauer spectra of Ph5Sb and Ph5Sb 1/2 C6H12 have been determined by Long et al.52 and IS values of 4.6 and 4.2 0.1 mm/s respectively have been reported. 

The inverted process, however, of transforming 1,6-diphosphahexa-1,5-diene b into 3,4-diphosphahexadiene or divinyl diphosphane proceeds under very mild conditions [Eq. (51)]. The diphosphide, prepared from succinylchloride and phenylbis(trimethylsilyl)phosphane between —70 and — 80°C, rearranges after silyl migration above 0°C, forming the spectroscopically detectable 1,6-diphosphahexadiene intermediate, and finally ending up with the divinyl diphosphane via a [3.3] sigmatropic bond shift (101). 

Trifluorovinylmagncsium iodide couples with chloro(diethoxy)phosphanc to give the trifluoro-vinylphosphane 32 in moderate yield and phenylbis(trifluoromethyl)phosphane (34) can be obtained by reacting chlorbis(trifluoromethyl)phosphanc (33) with phenylmagnesium bromide. ... 

There have been a number of new reports of reactions of this type including several involving addition to the aldehyde function of 161. Reaction with diphenyltrimethylsilylphosphine gave 162 while reaction with phenylbis (trimethylsilyl)phosphine gave 163 (Scheme 12) <2004TL6955>. 

Preparation.- Trialkyl or triaryl phosphites and trithiophosphites (55) can be obtained in 50-90% yields from white phosphorus, carbon tetrachloride, triethylamine, and the appropriate alcohol, phenol, or thiol in a polar aprotic solvent such as dimethylformamide. A series of racemic phenylbis(dialkylamino)phosphines (56) have been prepared in a one-pot synthesis as shown the bulk of the dicyclohexyl-amino group prevents substitution of the second chlorine atom, and the products (56) are claimed to be stable to air and moisture. In a one-pot synthesis tris(diethylamino)-phosphine has been treated successively with three different alcohols to give a 89% yield of the thiophosphate (57) after oxidation with sulphur. ... 

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