ChemInform Abstract: The Crystal Structure of Dicyclopentadienylmercury.

Fischer, B.; Mier, G. P. M. van; Boersma, J.; Koten, Gerard van; Smeets, W. J. J.; Spek, Anthony L.

doi:10.1002/chin.198826072

Cited by 7 publications

(9 citation statements)

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“…Zinc(II) chloride (97%), copper(I) chloride (99.99%), copper(I) iodide (99.999%), [ZnMe 2 ] (2.0 M in toluene), PPh 3 , and [LiN(SiMe 3 ) 2 ] were purchased from Aldrich and used as received. [{Ti(η 5 -C 5 Me 5 )(μ-NH)} 3 (μ 3 -N)] ( 1 ), , [ZnR 2 ] (R = CH 2 SiMe 3 , CH 2 Ph, N(SiMe 3 ) 2 , , C 5 H 4 SiMe 3 , C 5 H 5 ), [LiCH 2 SiMe 3 ], [Li(C 5 H 4 SiMe 3 )], [Li(C 5 H 5 )], [Li(C 9 H 7 )], and [{CuN(SiMe 3 ) 2 } 4 ] , were prepared according to published procedures.…”

Section: Methodsmentioning

confidence: 99%

Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper

et al. 2006

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Several azaheterometallocubane complexes containing [MTi3N4] cores have been prepared by the reaction of [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) with zinc(II) and copper(I) derivatives. The treatment of 1 with zinc dichloride in toluene at room temperature produces the adduct [Cl2Zn{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (2). Attempts to crystallize 2 in dichloromethane gave yellow crystals of the ammonia adduct [(H3N)Cl2Zn{(mu3-NH)Ti3(eta5-C5Me5)3(mu-NH)2(mu3-N)}] (3). The analogous reaction of 1 with alkyl, (trimethylsilyl)cyclopentadienyl, or amido zinc complexes [ZnR2] leads to the cube-type derivatives [RZn{(mu3-N)(mu3-NH)2Ti3(eta5-C5Me5)3(mu3-N)}] (R = CH2SiMe3 (5), CH2Ph (6), Me (7), C5H4SiMe3 (8), N(SiMe3)2 (9)) via RH elimination. The amido complex 9 decomposes in the presence of ambient light to generate the alkyl derivative [{Me3Si(H)N(Me)2SiCH2}Zn{(mu3-N)(mu3-NH)2Ti3(eta5-C5Me5)3(mu3-N)}] (10). The chloride complex 2 reacts with lithium cyclopentadienyl or lithium indenyl reagents to give the cyclopentadienyl or indenyl zinc derivatives [RZn{(mu3-N)(mu3-NH)2Ti3(eta5-C5Me5)3(mu3-N)}] (R = C5H5 (11), C9H7 (12)). Treatment of 1 with copper(I) halides in toluene at room temperature leads to the adducts [XCu{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (X = Cl (13), I (14)). Complex 13 reacts with lithium bis(trimethylsilyl)amido in toluene to give the precipitation of [{Cu(mu4-N)(mu3-NH)2Ti3(eta5-C5Me5)3(mu3-N)}2] (15). Complex 15 is prepared in a higher yield through the reaction of 1 with [{CuN(SiMe3)2}4] in toluene at 150 degrees C. The addition of triphenylphosphane to 15 in toluene produces the single-cube compound [(Ph3P)Cu{(mu3-N)(mu3-NH)2Ti3(eta5-C5Me5)3(mu3-N)}] (16). The X-ray crystal structures of 3, 8, 9, and 15 have been determined.

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Section: Methodsmentioning

confidence: 99%

Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper

et al. 2006

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“…t BuCpH 2 . A solution of 2-bromo-2-methylpropane (23.7 g, 173.3 mmol) in THF (90 mL) was heated to reflux, and then sodium cyclopentadienide (93.7 mL, 2.0 M in THF) was added dropwise over 1 h. The resulting dark red suspension was refluxed overnight and then poured into 100 mL of saturated NH 4 Cl. The organic layer was separated, and the aqueous layer was washed with Et 2 O (3 × 25 mL).…”

Section: Methodsmentioning

confidence: 99%

Ethylene/Norbornene Copolymerizations with Titanium CpA Catalysts

1999

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Group 4 ansa-cyclopentadienylamido (CpA) complexes [Me2Si(Cp‘)(NR)]MCl2 (R = alkyl, M = Ti, Zr) efficiently copolymerize ethylene with a variety of α-olefins. Ethylene/norbornene copolymerization reactivity ratios were determined at 40 °C for CpA catalysts [Me2Si(Cp‘)(N t Bu)]TiCl2 (Cp‘ = Me4Cp, 2,4-Me2Cp, 3- t BuCp, Ind), and the resulting values are low (r 1 = 2.0−5.1, r 2 → 0), suggesting a tendency toward alternating comonomer insertion at high norbornene/ethylene feed ratios. As reaction temperature is increased and norbornene concentration is decreased, productivity increases and norbornene incorporation decreases. No more than 46 mol % norbornene is incorporated into the copolymer using these CpA catalysts even at low feed ratios (E/N ≥ 0.02), and norbornene homopolymerizations with [Me2Si(Me4Cp)(N t Bu)]TiCl2 proceed to very low conversion (<1%). 13C NMR spectroscopy of CpA-derived poly(ethylene-co-norbornene)s shows the copolymers contain virtually no consecutive norbornene sequences, and the microstructure of the resulting ethylene norbornene copolymers is dependent on catalyst geometry.

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“…To overcome this disorder, the same synthetic procedure was used with the substituted cyclopentadienyl compounds bis(tert-butylcyclopentadienyl)zinc and bis[(trimethylsilyl) cyclopentadienyl]zinc 327 . Indeed, the corresponding Zn 4 Ni 2 clusters were formed, in which the geometry of the central cluster core and the bonding of the cyclopentadienyl groups to nickel is identical to that in 251.…”

Section: Organozinc Compounds Containing a Zinc-transitionmentioning

confidence: 99%