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• 2175-90-8 6,6-Diphenylfulvene 
• 90-99-3 diphenylchloromethane 
• 622-42-4 1-nitro-1-phenylmethane 

Relevant academic research and scientific papers

Half-sandwich complexes of titanium and zirconium with pendant phenyl substituents. The influence of ansa-aryl coordination on the polymerisation activity of half-sandwich catalysts

Benzyl-substituted Group 4 half-sandwich complexes (η5-C5H4R)TiCl3 (1a, R = CMe2Ph; 2a, R = CMe2CH2Ph; 4a, R = SiMe2Ph; 5a, R = CHPh2) are readily accessible from C5H4(R)SiMe3 and TiCl4, while the reaction of C5H4(CMe2CH2Ph)SiMe3 with ZrCl4(SMe2)2 affords (C5H4CMe2CH2Ph)ZrCl 3·dme (3a). The structures of 1a, 4a and 5a have been determined by X-ray diffraction; the compounds are monomeric in the solid state. Alkylation readily affords the corresponding trimethyl and tribenzyl derivatives; the crystal structure of (η5-C5H4CHPh2)Ti(CH 2Ph)3 (5b) has been determined. Treatment of (η5-C5H4R)MMe3 with [Ph3C]+[B(C6F5)4] - in dichloromethane at low temperatures generates cationic [(η5-C5H4R)MMe2]+ complexes; the complexes are stabilised by π-coordination to the phenyl ring to give ansa-arene complexes with one- and two-carbon linkages. The complexes catalyse the polymerisation of propene. Compared to the system Cp*TiMe3/B(C6F5)3 the ansa complexes show reduced catalytic activity and enhanced chain termination.

UEBERGANGSMETALL-FULVEN-KOMPLEXE. XXVIII. REAKTIONEN VON (FULVEN)Cr(CO)3-KOMPLEXEN UND Α-FERROCENYL-CARBENIUMIONEN MIT NUKLEOPHILEN

Tricarbonyl(fulvene)chromium complexes react with anionic nucleophiles to give functionally substituted cyclopentadienyl derivatives.The nucleophilic attack occurs at the exocyclic carbon atom of the fulvene ligand.Addition of PPh2- to (η6-6,6-dimethylfulvene)Cr(CO)3 (1) yields the novel anion 5-C5H4C(CH3)2PPh2)Cr(CO)3>-, which can be isolated as a K+, (C2H5)4N+, (C6H5)4P+, or Tl+ derivative (2-5).The potassium salt of the uncoordinated C5H4C(CH3)2PPh2- anion (7) is obtained by treatment of 6,6-dimethylfulvene with KPPh2*2C4H8O2.Similarly, NaC5H5 reacts with 1 to give Na5-C5H4C(CH3)2C5H5)Cr(CO)3> (8).The reactions of (6-dimethylaminofulvene)Cr(CO)3 (15) with nucleophiles are accompanied by elimination of dimethylamine.Addition of Ph3P=CH2 to 15 gives an unstable product, but after reaction of 6-dimethylaminofulvene with Ph3P=CH2, the free ligand C5H4=CHCH=PPh3 (17) can be isolated in moderate yields.Deeply colored anions of the type 5:η5-C5H4C(R)=C5H4)Cr2(CO)6>- (R = H, N(CH3)2 are synthesized by reaction of 15 or (6-dimethylamino-6-methylthiofulvene)Cr(CO)3 with NaC5H5 and subsequent complexation of the mononuclear intermediate with (CH3CN)3Cr(CO)3.In addition, the synthesis of the new fulvene complexes M(CO)3 (23,24; M = Cr, Mo) is described.The investigation is extended to α-ferrocenylcarbenium ions, which are isoelectronic with (fulvene)Cr(CO)3 complexes. 5-C5H5)Fe(C5H4CPh2)>+ BF4- (25) adds tertiary phosphines at the exocyclic carbon atom to give phosphonium salts of the type 5-C5H4)Fe(C5H4CPh2PR3)>+ BF4-.A CO-substitution product of a tricarbonyl(fulvene)chromium complex is obtained for the first time by irradiation of (η6-6,6-diphenylfulvene)Cr(CO)3 in the presence of PPh3.In addition, an improved synthesis of the (CH3CN)3M(CO)3 complexes (M = Cr, Mo, W) is reported.

REDUCTION OF 6,6-DISUBSTITUTED FULVENES WITH ALKALI METALS

Irrespective of the nature of the alkali metals and the solvent, the reduction of 6,6-disubstituted fulvenes with alkali metals is fairly selective and occurs at the exocyclic double bond to form substituted cyclopentadienes.The mechanism of such reactions is discussed.