“…The coordination sphere around the titanium center can be described as octahedral, with the oxygen atoms of the tbop ligand [O(11), O(21)] and of two bridging OEt groups [O(1), O(1A)] forming the equatorial plane, while the carbon atom [C(1)] of the methyl group and the sulfur link of the tbop ligand occupy the apical sites. The two Ti−O(aryloxo) distances of 1.896(2) and 1.916(2) Å are in the expected range for Ti(IV) complexes with facially coordinated bisaryloxo ligands. ,, The Ti−μ−O(ethoxo) distance of 1.992(2) Å is typical for Ti 2 (μ-OR) 2 moieties. , The Ti−C distance of 2.078(4) Å is similar to those observed in [Ti 2 (μ-OMe) 2 Me 2 (tritox) 2 ] [2.063(10) Å] and [Ti(mbp)Me 2 ] (mbp = 2,2‘-methylenebis(6- tert -butyl-4-methylphenolato) [2.090(9) and 2.030(10) Å] 11a. The Ti−S bond length of 2.985(1) Å is the longest among titanium complexes containing the sulfide-linked bisphenolato ligands. 2f,g,i,11e,12a 3 Molecular structure of 5 ·Et 2 O.…”
The tridentate (OSO-functions) biphenol, 2,2‘-thiobis{4-(1,1,3,3-tetramethylbutyl)phenol}
(tbopH2), reacts with AlMe3 to give [Al2(μ-tbop-κ3O,S,O)2Me2] (1). Alcoholysis of 1 results in
the formation of [Al2(μ-OEt)2(tbop-κ3O,S,O)2] (2). The reaction of 2 with TiCl4 gives the
trimeric complex [Ti3(μ-OEt)2(μ-tbop-κ3O,S,O)2Cl6] (3)·C6H14. Alkylation of 3·C6H14 with LiMe
produces two dimeric complexes, [Ti2(μ-tbop-κ3O,S,O)2Me4] (4) and [Ti2(μ-OE)2(tbop-κ3O,S,O)2Me2] (5)·Et2O. Treatment of [Ti2(μ-OEt)2(tbop-κ3O,S,O)2(OEt)2] with AlMe3 and EtOH afforded
the heterobimetallic species, [Ti2Al2(μ-OEt)6(μ-tbop-κ3O,S,O)2(OEt)4] (6). The structures of
1−6 were confirmed by NMR spectroscopy; complexes 1, 3·C6H14, 5·Et2O, and 6 were further
investigated by X-ray crystallography. Compounds 3−6, when supported on MgCl2 and
activated with aluminum alkyls, effectively polymerize ethene.
“…The coordination sphere around the titanium center can be described as octahedral, with the oxygen atoms of the tbop ligand [O(11), O(21)] and of two bridging OEt groups [O(1), O(1A)] forming the equatorial plane, while the carbon atom [C(1)] of the methyl group and the sulfur link of the tbop ligand occupy the apical sites. The two Ti−O(aryloxo) distances of 1.896(2) and 1.916(2) Å are in the expected range for Ti(IV) complexes with facially coordinated bisaryloxo ligands. ,, The Ti−μ−O(ethoxo) distance of 1.992(2) Å is typical for Ti 2 (μ-OR) 2 moieties. , The Ti−C distance of 2.078(4) Å is similar to those observed in [Ti 2 (μ-OMe) 2 Me 2 (tritox) 2 ] [2.063(10) Å] and [Ti(mbp)Me 2 ] (mbp = 2,2‘-methylenebis(6- tert -butyl-4-methylphenolato) [2.090(9) and 2.030(10) Å] 11a. The Ti−S bond length of 2.985(1) Å is the longest among titanium complexes containing the sulfide-linked bisphenolato ligands. 2f,g,i,11e,12a 3 Molecular structure of 5 ·Et 2 O.…”
The tridentate (OSO-functions) biphenol, 2,2‘-thiobis{4-(1,1,3,3-tetramethylbutyl)phenol}
(tbopH2), reacts with AlMe3 to give [Al2(μ-tbop-κ3O,S,O)2Me2] (1). Alcoholysis of 1 results in
the formation of [Al2(μ-OEt)2(tbop-κ3O,S,O)2] (2). The reaction of 2 with TiCl4 gives the
trimeric complex [Ti3(μ-OEt)2(μ-tbop-κ3O,S,O)2Cl6] (3)·C6H14. Alkylation of 3·C6H14 with LiMe
produces two dimeric complexes, [Ti2(μ-tbop-κ3O,S,O)2Me4] (4) and [Ti2(μ-OE)2(tbop-κ3O,S,O)2Me2] (5)·Et2O. Treatment of [Ti2(μ-OEt)2(tbop-κ3O,S,O)2(OEt)2] with AlMe3 and EtOH afforded
the heterobimetallic species, [Ti2Al2(μ-OEt)6(μ-tbop-κ3O,S,O)2(OEt)4] (6). The structures of
1−6 were confirmed by NMR spectroscopy; complexes 1, 3·C6H14, 5·Et2O, and 6 were further
investigated by X-ray crystallography. Compounds 3−6, when supported on MgCl2 and
activated with aluminum alkyls, effectively polymerize ethene.
“…The coordination geometry of titanium is tetrahedral with an O-Ti-O bite angle of 108.19-( 5)°. This is remarkable insofar as [Me 2 Ti(OCBu t 3 )(µ-OMe)] 2 , 20 in which the titanium is protected by the space demand of the tritox ligand, and [Me 2 Ti(OCHMeCH 2 Me 2 -CO)] 2 , 21 a cyclic dialkoxide that has the same ring size as 10, are dimeric in the solid state. The Ti-C(Me) distances in 10 with 2.0787(18) Å for Ti1-C2 and 2.0829( 19) Å for Ti1-C1 were found to be slightly shorter than that of {MeTi-[µ-(η 5 -C 5 Me 4 SiMe 2 O)]} 2 (µ-CH 2 ) 22 with 2.121 Å [Ti-C(Me)], which is to our knowledge the only known complex with a Si-O-Ti-Me bond sequence for which X-ray data are available.…”
Section: Synthesis and Reactivity Of {Sime 2 [(Me 3 Si)mentioning
The syntheses and structures of zirconium and titanium complexes containing the novel chelating trisilane-1,3-diolate ligand [Me2Si(R2SiO)2]2- (R = SiMe3) (5)-H2 are reported. The chloride complexes [Me2Si(R2SiO)2]TiCl2 (7a) and [Me2Si(R2SiO)2]ZrCl2 x 2 THF (7b) were prepared by the reaction of MCl4 (M = Ti, Zr) with [Me2Si(R2SiO)2]2Ti (6a) and [Me2Si(R2SiO)2]2Zr (6b), which are derived from the reaction of 5 with M(NEt2)4, respectively. In the presence of TiCl4, complexes 6a and 7a undergo a ring-opening reaction to produce the dinuclear complex [Me2Si(R2SiO)2][TiCl3]2 (9). [Me2Si(R2SiO)2]TiMe2 (10) and [Me2Si(R2SiO)2]TiBnz2 (11) were prepared in moderate yields from reactions of 7a with 2 equiv of MeMgBr and BnzMgCl, respectively. According to NMR spectroscopic investigations, the reaction of the dimethyltitanium complex 10 with B(C6F5)3 led to full exchange of both methyl groups by C6F5 groups under quantitative formation of [Me2Si(R2SiO)2]Ti(C6F5)2 (12) and a mixture of B(C6F5)(3-n)Me(n), where n = 1-3. The structure of 12 is further evidenced by the preparation of an identical sample from the reaction of 7a with 2 equiv of C6F5MgBr. Refluxing an ether solution of 12 surprisingly gave [Me2Si(R2SiO)2]2TiC6F5]2O (13) as a result of ether cleavage. The structures of the complexes 7a, 7b, 9, 10, and 13 were determined by X-ray crystallography, and structural discussion of the bond parameters will be given.
“…The determinations of solubility, in a variety of solvents and solvent mixtures, were made as follows. A saturated solution of Fe(phen)3(C104)2 was prepared by adding the complex salt to 5 ml of the solvent in a 10-ml ampoule at about 40°C until no more complex would dissolve. The ampoules were capped with rubber septum caps, suspended in an aquarium bath held at 25.0 dk 0.1 °C, and agitated continuously. The arrangement shook the ampoules vigorously enough to maintain the crystals of complex in suspension in the solutions.…”
A model for the solvation of the [Fe(phen)3]2+ cation is proposed based on the geometry of the complex. The solvation energy is considered to be the sum of two parts: that due to the ion-dipole interaction with the solvent and that due to the van der Waals interaction between the solvent and the aromatic ligands. The model was tested, and verified, by measuring the solubilities of Fe(phen)3(C104)2 and naphthalene in ten pure solvents, and in mixtures of water with methanol, acetone, and JV.TV-dimethylformamide. The van der Waals interaction with the ligands was shown to parallel the interaction with naphthalene. The NMR chemical shifts of the 5,6 protons on Fe(phen)32+ were measured in some of the solvent systems.
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