Crystal and molecular structure and properties of tetramesitylvanadium

Głowiak, Tadeusz; Grobelny, R.; Jeżowska-Trzeblatowska, B.; Kreisel, Günter; Seidel, W.; Uhlig, E.

doi:10.1016/s0022-328x(00)90419-4

Cited by 31 publications

(12 citation statements)

References 18 publications

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“…[19] The EPR spectroscopic data of compounds 4-6, which can be satisfactorily explained by this structural proposal (see below) are in keeping with this assumption. …”

supporting

confidence: 63%

“…: [19] the CÀVÀC angles in this species take values between 96.4(3)8 and 117.8(3)8 and the VÀC distances are slightly shorter (207.1(6)-209.5(7) pm) than those found in 1', as would be expected with an increase in the oxidation state of the metal centre. All the C 6 Cl 5 rings in the Scheme 1.…”

mentioning

confidence: 52%

“…VÀC (1) 214.5(5) C(13)ÀC (14) 139.7(7) VÀC (7) 216.8(5) C(13)ÀC (18) 138.4(6) VÀC (13) 213.6(5) C (14)ÀF (14) 135.7(5) VÀC (19) 219.3(5) C(18)ÀF (18) 136.3(5) VÀC (25) 221.7(5) C(19)ÀC (20) 138.1(7) C(1)ÀC (2) 137.5(6) C(19)ÀC (24) 138.4(7) C(1)ÀC (6) 136.3(6) C(20)ÀF (20) 138.0(5) C(2)ÀF (2) 135.9(5) C (24)ÀF (24) 137.0(5) C(6)ÀF (6) 136.8 (5) C (25)ÀC (26) 138.4(7) C(7)ÀC (8) 137.7 (7) C (25)ÀC (30) 137.1(7) C(7)ÀC (12) 139.0 (7) C (26)ÀF (26) 137.3(6) C(8)ÀF (8) 136.9(5) C(30)ÀF (30) 137.1(5) C(12)ÀF (12) 135.4 (5) Bond angles C(1)ÀVÀC (7) 127.1(2) C(8)ÀC (7)ÀC (12) 111.6(4) C(1)ÀVÀC (13) 107.3(2) C (7)ÀC (8)ÀF (8) 120.0(4) C(1)ÀVÀC (19) 99.5(2) C (7)ÀC (12)ÀF (12) 120.0(4) C(1)ÀVÀC (25) 82.1(2) VÀC (13)ÀC (14) 124.6(4) C(7)ÀVÀC (13) 125.4 (2) VÀC (13)ÀC (18) 122.9(4) C(7)ÀVÀC …”

Section: Bond Lengthsmentioning

confidence: 99%

“…The signal at g % 2 observed in some of these measurements can be assigned to small amounts of oxidised V IV species (see below). (24) 138.9(7) C(1)ÀC (2) 139.2 (7) C (20)ÀCl (20) 174.5(6) C(1)ÀC (6) 138.7 (7) C (24)ÀCl (24) 174.5 (6) Bond angles C(1)ÀVÀC (7) 112.1(2) C(8)ÀC (7)ÀC (12) 114.4(5) C(1)ÀVÀC (13) 117.6(2) C (7)ÀC (8)ÀCl (8) 117.1(5) C(1)ÀVÀC (19) 101.1(2) C (7)ÀC (12)ÀCl (12) 119.7(4) C(7)ÀVÀC (13) 98.1(2) VÀC (13)ÀC (14) 130.7(4) C(7)ÀVÀC (19) 116.1(2) VÀC (13)ÀC (18) 115.6(4) C(13)ÀVÀC (19) 112.6(2) C(14)ÀC (13)ÀC (18) 113.5(5) VÀC(1)ÀC (2) 130.6(4) C(13)ÀC (14)ÀCl (14) 119.7(4) VÀC(1)ÀC (6) 115.2(4) C(13)ÀC (18)ÀCl (18) 116.9(4) C(2)ÀC (1) Figure 2. Room-temperature X-band EPR spectra of polycrystalline samples of 1, 1', 2 and 3.…”

mentioning

confidence: 99%

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New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

Alonso

Forniés

García‐Monforte

et al. 2005

Chemistry A European J

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The arylation of [VCl3(thf)3] with LiR(Cl), where R(Cl) is a polychlorinated phenyl group [C6Cl5, 2,4,6-trichlorophenyl(tcp), or 2,6-dichlorophenyl (dcp)] gives four-coordinate, homoleptic organovanadium(III) derivatives with the formula [Li(thf)(4)][V(III)(R(Cl))(4)] (R(Cl) = C(6)Cl(5) (1), tcp (2), dcp (3)). The anion [V(III)(C6Cl5)4]- has an almost tetrahedral geometry, as observed in the solid-state structure of [NBu4][V(C6Cl5)4] (1') (X-ray diffraction). Compounds 1-3 are electrochemically related to the neutral organovanadium(IV) species [V(IV)(R(Cl))4] (R(Cl) = C6Cl5 (4), tcp (5), dcp (6)). The redox potentials of the V(IV)/V(III) semisystems in CH2Cl2 decrease with decreasing chlorination of the phenyl ring (E(1/2) = 0.84 (4/1), 0.42 (5/2), 0.25 V (6/3)). All the [V(IV)(R(Cl))4] derivatives involved in these redox couples could also be prepared and isolated by chemical methods. The arylation of [VCl(3)(thf)(3)] with LiC6F5 also gives a homoleptic organovanadium(III) compound, but with a different stoichiometry: [NBu4]2[V(III)(C6F5)5] (7). In this five-coordinate species, the C6F5 groups define a trigonal bipyramidal environment for the vanadium atom (X-ray diffraction). EPR spectra for the new organovanadium compounds 1-6 are also given and analysed in terms of an elongated tetrahedral structure with C(2v) local symmetry. It is suggested that the R(Cl) groups exert a protective effect towards the vanadium centre.

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“…[19] The EPR spectroscopic data of compounds 4-6, which can be satisfactorily explained by this structural proposal (see below) are in keeping with this assumption. …”

supporting

confidence: 63%

mentioning

confidence: 52%

Section: Bond Lengthsmentioning

confidence: 99%

mentioning

confidence: 99%

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New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

Alonso

Forniés

García‐Monforte

et al. 2005

Chemistry A European J

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“…, [51] containing s-bound aryl groups, were found to exhibit similar overall geometries (Table 3). (7) 220.7(4) C(1)-Ti-C(7) 116.8(2) C(1)ÀC (2) 139.4(6) C(1)-Ti-C(7') 114.0(2) C(1)ÀC (6) 140.6(6) C(1')-Ti-C(7) 114.0(2) C(2)ÀCl (2) 175.0(5) C(1')-Ti-C(7') 116.8(2) C(6)ÀCl (6) 174.9(5) C(7)-Ti-C(7') 97.9(2) Ti¥¥¥Cl (2) 305.0(4) Ti-C(1)-C(2) 113.0(3) Ti¥¥¥Cl (6) 377.3(4) Ti-C(1)-C(6) 133.8(3) C (7)ÀC (8) 140.0(7) C(2)-C(1)-C(6) 113.2(4) C (7)ÀC (12) 139.4(7) (17) 144.4 (7) O (20) 143…”

mentioning

confidence: 90%

Synthesis and Characterization of Pentachlorophenyl–Metal Derivatives with d⁰ and d¹⁰ Electron Configurations

Ara

Forniés

García‐Monforte

et al. 2004

Chemistry A European J

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By reaction of [TiCl(3)(thf)(3)] with LiC(6)Cl(5), the homoleptic organotitanium(III) derivative [Li(thf)(4)][Ti(III)(C(6)Cl(5))(4)] (1) has been prepared as a paramagnetic (d(1), S = 1/2, g(av) = 1.959(2)), extremely air-sensitive compound. Oxidation of 1 with [N(C(6)H(4)Br-4)(3)][SbCl(6)] gives the diamagnetic (d(0)) organotitanium(IV) species [Ti(IV)(C(6)Cl(5))(4)] (2). Compounds 1 and 2 are also electrochemically related (E(1/2) = 0.05 V). The homoleptic, diamagnetic (d(10)) compounds [N(PPh(3))(2)][Tl(C(6)Cl(5))(4)] (3) and [Sn(C(6)Cl(5))(4)] (4) have also been prepared. Nearly tetrahedral environments have been found for the d(0), d(10), and d(1) metal centers in the molecular structures of compounds 2-4 as well as in that of [Li(thf)(2)(OEt(2))(2)][Ti(III)(C(6)Cl(5))(4)].CH(2)Cl(2) (1') (X-ray diffraction). The reaction of the heavier Group 4 metal halides, MCl(4) (M = Zr, Hf) with LiC(6)Cl(5) in the presence of [NBu(4)]Br gives, in turn, the heteroleptic species [NBu(4)][M(C(6)Cl(5))(3)Cl(2)] (M = Zr (5), Hf (6)). Compounds 5 and 6 are isomorphous and isostructural, with the metal center in a trigonal-bipyramidal (TBPY-5) environment defined by two axial Cl ligands and three equatorial C(6)Cl(5) groups (X-ray diffraction). No redox features are observed for compounds 3-6 in CH(2)Cl(2) solution between -1.6 and +1.6 V.

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Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Hirao

2005

Encyclopedia of Inorganic Chemistry

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Crystal and molecular structure and properties of tetramesitylvanadium

Cited by 31 publications

References 18 publications

New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

Synthesis and Characterization of Pentachlorophenyl–Metal Derivatives with d⁰ and d¹⁰ Electron Configurations

Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Crystal and molecular structure and properties of tetramesitylvanadium

Cited by 31 publications

References 18 publications

New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour

Synthesis and Characterization of Pentachlorophenyl–Metal Derivatives with d0 and d10 Electron Configurations

Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Synthesis and Characterization of Pentachlorophenyl–Metal Derivatives with d⁰ and d¹⁰ Electron Configurations