∑-Alkenyl and halogeno complexes of vanadium (I and II). The crystal structures of (C1V(CO)2(Ph2PCH2CH2PEt2)2 · benzene, Br2V(Me2PCH2CH2PMe2)2 and I2V(Me2PCH2CH2PMe2)2 · toluene

Süssmilch, Frank; Olbrich, Falk; Gailus, Hartmut; Rodewald, Dieter; Rehder, Dieter

doi:10.1016/0022-328x(94)80199-1

Cited by 19 publications

(4 citation statements)

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“…The molecule crystallized in the space group P 2 1 / n with the vanadium atom resting on a center of inversion. The V−P distances and P−V−P angles are normal for trans -(DMPE) 2 VX 2 compounds. − At 2.6408(6) Å, the V−Se interaction is on the long side, but not unexpectedly so, considering the low formal oxidation state of the metal. As observed for related species with trans -L 4 M[ESi(SiMe 3 ) 3 ] 2 geometries, , the V−Se−Si angle of 145.62(5)° is on the high end of the range observed for complexes of this ligand.…”

Section: Resultsmentioning

confidence: 99%

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Homoleptic Selenolates of Vanadium(II), -(III), and -(IV): Generation, Trapping, and Disproportionation of Tris[tris(trimethylsilyl)silylselenolate]vanadium

Gerlach

Arnold

1998

Inorg. Chem.

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Homoleptic selenolates of V(II) and V(IV) are prepared by selenolysis of the amide ligands in [(Me3Si)2N]2VSeSi(SiMe3)3 with 2 equiv of HSeSi(SiMe3)3. The products were isolated by fractional crystallization from a mixture of hexanes/HMDSO (HMDSO = hexamethyldisiloxane), which first gave a V(II) selenolate of empirical composition V[SeSi(SiMe3)3]2(HMDSO)1/2, followed by the more soluble monomeric V(IV) species, V[SeSi(SiMe3)3]4. These compounds are proposed to be the disproportionates of a V(III) precursor (i.e. “V[SeSi(SiMe3)3]3”). Room-temperature EPR spectra of the tetraselenolate exhibited an 8-line pattern typical of V(IV) with g iso = 1.92 and A iso = 65 G. Addition of 2 equiv of DMPE (DMPE = 1,2-bis(dimethylphosphino)ethane) to the V(II) selenolate afforded trans-(DMPE)2V[SeSi(SiMe3)3]2 which has been characterized by X-ray crystallography. “V[SeSi(SiMe3)3]3” can be generated in cold hexanes and trapped with Lewis bases to afford the 4-coordinate adducts V[SeSi(SiMe3)3]3(L) (L = pyridine, 2,6-dimethylphenylisocyanide). For L = pyridine, addition of styrene oxide resulted in a 2-electron oxidation and formation of diamagnetic OV[SeSi(SiMe3)3]3. Reaction of 1/2 equiv of pyrazine with “V[SeSi(SiMe3)3]3” gave the pyrazine-bridged dimer {V[SeSi(SiMe3)3]3}2(μ-pyrazine) which was also crystallographically characterized.

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Section: Resultsmentioning

confidence: 99%

“…The V-P distances and P-V-P angles are normal for trans-(DMPE) 2 VX 2 compounds. [41][42][43][44] At 2.6408(6) Å, the V-Se interaction is on the long side, but not unexpectedly so, considering the low formal oxidation state of the metal. As observed for related species with trans-L 4 M[ESi(SiMe 3 ) 3 ] 2…”

Section: Resultsmentioning

confidence: 99%

Homoleptic Selenolates of Vanadium(II), -(III), and -(IV): Generation, Trapping, and Disproportionation of Tris[tris(trimethylsilyl)silylselenolate]vanadium

Gerlach

Arnold

1998

Inorg. Chem.

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“…The most reported metal‐alkenyl complexes are Pt, Ti and Fe, whereas complexes with other metals such as Ni, Hf, Rh, Mo, Co, Pd, Ru and Zr have been the subject of only a few reports. Various σ‐alkenyl complexes of vanadium of the type (alkenyl)V(CO) 6− n P m (where n = 2, 3 and P m is a potentially m ‐dentate phosphine coordinated through n of its donor centers, n ≤ m ) were reported by photo‐induced hydrovanadation of the alkynes 2‐butyne, 1‐hexyne, 3‐hexyne and 3,3‐dimethyl‐1‐butyne . A series of σ‐alkenyl ruthenium complexes bearing both sulfur and nitrogen donors as ligands have been synthesized.…”

Section: Methodsmentioning

confidence: 99%

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Sravani

Venkatesh

Vijayakrishna

et al. 2014

Applied Organom Chemis

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Intermediates for many catalysis reactions reported in the literature are metal‐alkyl and metal‐alkenyl, including metallacycloalkane species. Synthesis and reactions of metal‐alkyl, alkenyl and metallacyle complexes have shown a great deal of development during the past few decades. This review summarizes the significant contributions reported on metal‐alkenyl compounds, specifically those containing at least a carbon chain with pendant alkene group [M―CH2CH2CHCH2]. Although metal‐alkenyl complexes are stable with strong chelating diphosphines and with a decrease in the ligand donor strength, the complexes can decompose without any ambiguity. For example, platinum‐dialkenyl complexes react readily via β‐hydrogen elimination and reductive elimination promoted by the nature of the ligand, solvent and length of carbon chains. These complexes can also undergo intramolecular irreversible isomerization and this leads to the selective catalytic isomerization of 1‐alkenes to 2‐alkenes in the presence of platinum‐dialkenyl complexes as catalysts. Perhaps the most striking manifestations of flexibility are the facile and complete intramolecular and intermolecular alkene metathesis to yield the corresponding metallacycloalkenes in the presence of Grubbs’ catalysts. The diverse chemical reactivity of these complexes demonstrates both the scope and complexity of metal‐alkenyl chemistry depending on the nature of ligand and metal. Copyright © 2014 John Wiley & Sons, Ltd.

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“…The available information on structurally characterized bromidovanadium complexes is comparatively low. Examples include the V I complex [VBr(dmpe) 2 (Me 3 SiOC≡COSiMe 3 )] [dmpe = bis(dimethylphosphanyl)ethane],4 the V II complexes cis ‐[VBr 2 (bppa)] [bppa = bis(picolyl)‐oxobenzylamine],15a trans ‐[VBr 2 (C–N–C)thf] [C–N–C = 2, 6‐bis(imidazolydene)pyridine],15b trans ‐[VBr 2 (dmpe) 2 ]15c and trans ‐[VBr 2 (CN t Bu) 4 ],15d the V III complexes trans ‐[VBr 2 (CH 3 CN) 4 ] + ,16a trans ‐[VBr 2 (teg)] + (teg = tetraethyleneglycol),16b [VBr(OMes) 2 (thf) 2 ] (Mes = mesityl)16c and [VBr(NS 2 S′ 2 )] [NS 2 S′ 2 = bis(mercaptophenylthio)pyridine],16d the V IV complexes cis ‐[VBr 2 (S 2 CNEt 2 ) 2 ]17a and [VOBr(tpa)] + [tpa = tris(2‐pyridyl)amine],17b and finally the V V complexes trans ‐[VBr 2 ( cyclo ‐thiazene)(py) 2 ]18a (py = pyridine) and [VOBr 4 ] – 18b…”

Section: Introductionmentioning

confidence: 99%

Bromidovanadium(II, III, and IV) Complexes

Rehder¹,

Nekola²,

Behrens³

et al. 2013

Zeitschrift anorg allge chemie

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∑-Alkenyl and halogeno complexes of vanadium (I and II). The crystal structures of (C1V(CO)2(Ph2PCH2CH2PEt2)2 · benzene, Br2V(Me2PCH2CH2PMe2)2 and I2V(Me2PCH2CH2PMe2)2 · toluene

Cited by 19 publications

References 28 publications

Homoleptic Selenolates of Vanadium(II), -(III), and -(IV): Generation, Trapping, and Disproportionation of Tris[tris(trimethylsilyl)silylselenolate]vanadium

Homoleptic Selenolates of Vanadium(II), -(III), and -(IV): Generation, Trapping, and Disproportionation of Tris[tris(trimethylsilyl)silylselenolate]vanadium

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Bromidovanadium(II, III, and IV) Complexes

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