Addition compounds of niobium(IV) halides formed with monodentate alkyl sulfides. Synthesis, spectra, and magnetism

Hamilton, James B.; McCarley, Robert E.

doi:10.1021/ic50088a008

Cited by 17 publications

(10 citation statements)

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“…NbCl,(Haza), exhibits a slightly split band at -320 cm-I for v(Nb--Cl). More complex patterns are usually observed for NbC14L2 and TaC14L2 compounds and since four infrared-active bands are expected for the cis isomer (C2,) (54, 5 3 , this geometry has been proposed (22,30,31). The presence of a single band here would be consistent with a trans structure (D,,,), in which case the slight splitting of the only infrared-active E, mode would be due to solid-state effects.…”

Section: Infrared Spectroscopymentioning

confidence: 52%

“…The magnetic moment (1.36 BM) corresponds to a monomeric octahedral species (1). From the available data on NbCl,L, and TaC14L2 compounds (7,22,(29)(30)(31)(32)(33), there seems to be a preference for small monodentate ligands to give the cis isomer, although trans compounds are also known. In the present case, a single slightly split v(Nb-"Occupancy factor = 0.50. b~i t e statistically occupied by 0 and C1 atoms.…”

Section: Reactants and Techniquesmentioning

confidence: 99%

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Reactions of 7-azaindole with niobium and tantalum pentachlorides and coupling to the azaindolyl-azaindolium cation

Poitras¹,

Beauchamp²

1994

Can. J. Chem.

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JACQUES POITRAS and AND& L. BEAUCHAMP. Can. J. Chem. 72, 1675Chem. 72, (1994. The reaction of NbC1, and TaC1, with 7-azaindole (Haza) at room temperature in benzene or dichloromethane yielded MCl,(Haza) addition compounds. Under more severe conditions, the same compound was obtained with TaCl,. For NbCl,, some reduction to Nb(IV) was observed and NbCI,(Haza), NbCI,(Haza),, and the (H,aza)' ion were identified in the reaction mixture by infrared spectroscopy. Oxidative coupling of two azaindole units via N7-C6 also took place during the reaction, since the 7-(azaindol-6-y1)azaindolium cation was found as counter-ion in the crystal structures of two complex salts. In the crystals of

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Section: Infrared Spectroscopymentioning

confidence: 52%

Section: Reactants and Techniquesmentioning

confidence: 99%

Reactions of 7-azaindole with niobium and tantalum pentachlorides and coupling to the azaindolyl-azaindolium cation

Poitras¹,

Beauchamp²

1994

Can. J. Chem.

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“…After an early study, 79 the chemistry of Nb(IV) halides with chalcogenoethers was largely neglected.…”

Section: Niobium(iv and Tantalum(iv)mentioning

confidence: 99%

Developments in the chemistry of the hard early metals (Groups 1–6) with thioether, selenoether and telluroether ligands

2016

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The coordination chemistry of neutral thio-, seleno-and telluroether ligands towards the hard s-block, f-block and higher oxidation state early d-block metals has developed significantly over the 15 or so years. This has revealed several hitherto unknown classes of complexes and new insights into the chemistries of these hard-soft metal-ligand combinations. This Perspective describes the synthetic routes used to access such complexes and draws out their key structural features and spectroscopic properties. Where appropriate, applications of these species are also highlighted, including their use as single source precursors for the chemical vapour deposition of semiconducting metal chalcogenide thin films and as pre-catalysts for olefin polymerisation reactions. IntroductionThioether and selenoether ligands, which are neutral sulfur and selenium donors respectively, were for many years viewed as modest σ-donor ligands that formed complexes with the softer later d-block elements in low or medium oxidation states, or with post transition metals such as silver or mercury.1,2Complexes of the early d-block metals were mostly limited to low valent organometallics or carbonyls. The chemistry of telluroethers was very little explored, in major part a reflection of their limited availability and, for the alkyl telluroethers in particular, their extremely malodorous nature. 2,3The R2Te ligands are also oxygen sensitive (in contrast to the air stable R2S or R2Se), modest reducing agents and prone to cleavage of the CTe bond upon reaction with some metal centres. Even today, their chemistry remains much less extensive than that of their lighter analogues. 4 Major developments in the syntheses and coordination chemistry of macrocyclic thioethers considerably extended the range and stability of complexes containing metal centres across the d-block. More recent work has resulted in complexes of chalcogenoethers with many of the p-block elements,

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“…Diamagnetic /3-diketonate and carboxylate ditantalum complexes which are potentially of the edgesharing bioctahedral class have been reported by Hubert-Pfalzgraf and coworkers50 through ligand substitution reactions involving loss of HC1 (eq 29 and 30; p/ = NC5H4-p-Me). In both cases the released HC1 was Ta2Cl6(py/)4 + >4Me3CCOCH2COCMe3 -Ta2Cl4(Me3CCOCHCOCMe3)4 + Hpy/+Cl- (29) Ta2Cl6(py/)4 + Me3CC02H -Ta2Cl4(02CCMe3)4-2Me3CC02H + Hpy'+Cl- (30) trapped by the 4-methylpyridine and the pyridinium salt removed by sublimation or washing. The dipivaloylmethanato complex (65% yield) exhibited a single CMe3 resonance in the 7H NMR spectrum, whereas the spectra of the pivalate complex (80% yield) showed two solution species, with one having two in- Dinuclear complexes in which two square antiprismatic metal coordination spheres share a common 4fold face, and thus have four bridging ligands, make up a small but growing class of metal-metal singly bonded diniobium(IV) and ditantalum(IV) species.…”

Section: Edge-sharing Bioctahedral Complexes With Monodentate Ligandsmentioning

confidence: 99%

Metal-metal bonded dinuclear and organodimetallic complexes of the early transition metals (Groups 4 and 5): synthesis, structure, and reactivity

Messerle¹

1988

Chem. Rev.

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Addition compounds of niobium(IV) halides formed with monodentate alkyl sulfides. Synthesis, spectra, and magnetism

Cited by 17 publications

References 0 publications

Reactions of 7-azaindole with niobium and tantalum pentachlorides and coupling to the azaindolyl-azaindolium cation

Reactions of 7-azaindole with niobium and tantalum pentachlorides and coupling to the azaindolyl-azaindolium cation

Developments in the chemistry of the hard early metals (Groups 1–6) with thioether, selenoether and telluroether ligands

Metal-metal bonded dinuclear and organodimetallic complexes of the early transition metals (Groups 4 and 5): synthesis, structure, and reactivity

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