Organometallic nitrosyl chemistry. 43. Synthesis, characterization, and physical properties of unusual cyclopentadienyl bis(benzyl) nitrosyl complexes of molybdenum and tungsten

Legzdins, Peter; Jones, Richard H.; Phillips, Everett C.; Yee, Vivien C.; Trotter, James; Einstein, Frederick W. B.

doi:10.1021/om00050a034

Cited by 43 publications

(25 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Modelling this process (C 2 -C 2V ) results in a Gibbs free energy of activation of DG ‡ E 61.26 kJ mol À1 . 44,45 This is very close to that calculated for 4 (DG ‡ E 60.94 kJ mol À1 ), which shows analogous behaviour over the temperature range. The carboxylate carbon shift of 3 is in excellent agreement with that observed in CpTi(O 2 CMe) 3 and almost identical to 4 (d = 188.5, 189.2 and 188.6 ppm respectively).…”

supporting

confidence: 81%

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes

et al. 2015

View full text Add to dashboard Cite

show abstract

supporting

confidence: 81%

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes

et al. 2015

View full text Add to dashboard Cite

show abstract

“…The third benzyl ligand has a Zr-C-Ph angle of 102.0(13) ° suggesting an intermediate interaction between the aromatic fragment and the metal centre. Several transition metal complexes showing different modes of ligation of the benzyl ligands have been structurally characterized [28,[38][39][40]. The three C o~ atoms are bonded to Zr at the same distance, 2.27 A (average value) and define a plane almost parallel to the Cp ring plane.…”

Section: Description Of the Crystal Structure Of [Zr(~l 5-c 5 H4(simementioning

confidence: 99%

“…for C20H33N2Si3Zr: C, 41.17; H, 5.66; N, 4.80. Found: C, 40.91, H, 5.57; N, 4.62. 1H NMR (C6D6): ~ 6.9--6.7 (m, 5H, C6H5) , 6.78 (t, 2H, J~an = 2.56 Hz, C5H4), 6.52 (t, 2H, JnH = 2.56 Hz, CsH~), 0.95 (s, 6H, SiMe~), -0.04 (s, 18H, SiMe3).…”

Section: Synthesis Of [Zr{rls-csh4(sime2cl)} -(C(ph)[n(sime3)]2 } C12mentioning

confidence: 99%

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zrη5-C5H4 (SiMe2CH2Ph)(CH2Ph)3]

Ciruelo¹,

Cuenca²,

Gómez³

et al. 1997

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

New silyl substituted monocyclopentadienyl complexes of Zr(IV) were synthesized from the precursor [Zr{@-CsH4(SiMe2C1)}CI 3] (1). The reaction of 1 with the lithium benzamidinate salt Li[C(Ph){N(SiMe3)} 2] leads to the complex [Zr{r/5-CsHa(SiM%C1)}{C(Ph)[N(SiMe3)]2}C12 ] (2), which decomposes slowly in solution with elimination of SiMe3C1. Complex 1 reacts with alkyl, amido and alkoxo transfer reagents (4 equiv.) to afford complexes [Zr{@-CsH4(SiMe2X)}X 3] (X = NMe 2 (3), OSiMe 3 (4), CH2CMe2Ph (5), C6H 5 (6), C6F 5 (7) and CH2SiMe 3 (8)) in good yields. Compounds 6 and 7 retain diethyl ether used as solvent but decompose as soon as they are desolvated under high vacuum conditions. Reaction of 1 with Mg(CH2Ph) 2 • 2THF (4 equiv.) yields the tetrabenzyl complex [Zr{@-CsHa(SiMe2CH2Ph)}(CH2Ph) 3] (9). The lH and 13C NMR data of the latter compound are discussed in terms of the non-classical coordination mode of the CH 2 Ph ligand, The molecular structure of [Zr{~75-C 5H4(SiMe2CH 2 Ph)}(CH2 Ph)3] 9 has been determined by X-ray diffraction methods. The coordination geometry around the zirconium atom shows a substituted @-cyclopentadienyl ring and three different benzyl ligands: a distorted ~2-benzyl group; a normal r/l-benzyl group; and a benzyl ligand with an intermediate coordination mode. The benzyl fragment bonded to silicon points away from the metal center. 9 crystallized in monoclinic space group P21/c with a = 11.268(3) A, b = 10.846(3) A, c = 27.734(6) A, /3 = 100.29(1) °, V = 3334.9(15) ~3 for Z = 4. The tetraalkylated compounds 6, 7 and 9 are excellent precursors for the preparation of the chloro derivatives. Reactions of these complexes with 3 equiv, of HC1 gave the corresponding trichloro [Zr{@-CsH4(SiMezR)}C13] (R = C6H 5 (10), C6F' 5 (11), CHePh (12)). The monochloro [Zr{@-CsH4(SiM%CH2Ph)}(CH2Ph)2C1] (13) and the dichloro derivative [Zr{@-CsH4(SiMezCHzPh)}(CHzPh)C12] (14) are observed, at 60°C and 90°C, respectively, by NMR experiments in deuterated chloroform. Complexes 10 and 11 also retain coordinated solvent, decomposing slowly when it is removed. 1 and 12 in the presence of MAO as cocatalyst, at 25°C and 1 atm of monomer pressure, cause the polymerization of ethylene with moderate activities, while under similar conditions, polymerization of propylene and styrene proceeds giving only traces of atactic materials. © 1997 Elsevier Science S.A.

show abstract

“…The structure and reactivity of transition metal compounds containing benzyl ligands are often much different from similar compounds containing alkyl ligands owing to the ability of benzyl to involve more than one electron in metal bonding, giving rise to n compounds with n > 1 (Scholz et al, 1993;Legzdins et al, 1991;Pellecchia, Immirzi, Pappalardo & Peluso, 1994). In particular, coordinatively unsaturated benzyl derivatives of group 4 elements are widely studied for their catalytic behaviour in stereospeci®c polymerization Pellecchia, Immirzi & Zambelli, 1994).…”

Section: Introductionmentioning

confidence: 99%

Structures of Homoleptic Benzyl Derviatives of Zirconium

Tedesco¹,

Immirzi²,

Proto³

1998

Acta Crystallogr Sect B

View full text Add to dashboard Cite

Crystals of Zr(p-CH 2 C 6 H 4 CMe 3 ) 4 , tetra(4-tert-butylbenzyl)zirconium (1), have been studied by X-ray diffraction. The crystals belong to the tetragonal system, space group I4 Å , with a = 16.481 (2), c = 7.131 (4) A Ê , so that chemically equivalent ligands are also structurally equivalent, unlike other known homoleptic M(CH 2 -C 6 H 5 ) 4 compounds. ZrÐCH 2 ÐC ipso bond angles of 90.0 (2) suggest that ligands are 2 -bonded. The structure is discussed along with that of Zr(CH 2 C 6 H 5 ) 4 , tetrabenzylzirconium (2) (redetermined), which is crystallographically unsymmetrical but also of approximate S 4 symmetry. The distortion of (2) from tetragonal symmetry (the four ZrÐCH 2 ÐC ipso bond angles being rather different) is discussed along with crystal packing.

show abstract

Organometallic nitrosyl chemistry. 43. Synthesis, characterization, and physical properties of unusual cyclopentadienyl bis(benzyl) nitrosyl complexes of molybdenum and tungsten

Cited by 43 publications

References 0 publications

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zrη5-C5H4 (SiMe2CH2Ph)(CH2Ph)3]

Structures of Homoleptic Benzyl Derviatives of Zirconium

Contact Info

Product

Resources

About

Organometallic nitrosyl chemistry. 43. Synthesis, characterization, and physical properties of unusual cyclopentadienyl bis(benzyl) nitrosyl complexes of molybdenum and tungsten

Cited by 43 publications

References 0 publications

Double CO2 activation by 14-electron η8-permethylpentalene titanium dialkyl complexes

Double CO2 activation by 14-electron η8-permethylpentalene titanium dialkyl complexes

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zrη5-C5H4 (SiMe2CH2Ph)(CH2Ph)3]

Structures of Homoleptic Benzyl Derviatives of Zirconium

Contact Info

Product

Resources

About

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes

Double CO₂ activation by 14-electron η⁸-permethylpentalene titanium dialkyl complexes