The reactions of niobium and tantalum pentachlorides with triphenylphosphine and triphenylarsine oxides

Copley, D.B.; Fairbrother, Fred; Thompson, A.

doi:10.1016/0022-5088(65)90109-8

Cited by 41 publications

(9 citation statements)

References 16 publications

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“…This is particularly true in the case of the metal halides of the group 5 metals in the highest oxidation state, MX 5 (M = Nb, Ta). [1] For instance, deoxygenation reactions [2] have been reported with these powerful Lewis acids, and examples include sulfoxides, [3] phosphane oxides, [4] and crown ethers. [5] Therefore, the coordination chemistry of MX 5 (M = Nb, Ta) with oxygen donor ligands is scarcely developed, if we except alcohols or diols.…”

Section: Introductionmentioning

confidence: 99%

Complexes of Niobium(V) and Tantalum(V) Halides with Ligands that Contain N–C=O and P=O Functionalities: A Synthetic and Structural Study

2008

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Keywords: Niobium / Tantalum / Halides / Amide / P=O ligands / X-ray structureThe reactions of niobium and tantalum pentahalides, MX 5 , with dialkylureas (tetramethyl-and tetraethylurea, TMU and TEU, respectively), amides (N,N,dimethylformamide, DMF, N,N-diethylformamide, DEF, N-phenylacetamide, PhA), and P=O-containing compounds (triphenylphosphane oxide, TPPO, and trimethyl phosphate, TMP) are not dependent on the reactant to metal molar ratio, and afford hexacoordinate complexes of the general formula MX 5 (L). The only exception is given by the reaction of TaBr 5 with TMU, which proceeds by bromide migration from one metal center to another, and provides the ionic adduct [TaBr 4 (TMU) 2 ][TaBr 6 ].

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Section: Introductionmentioning

confidence: 99%

Complexes of Niobium(V) and Tantalum(V) Halides with Ligands that Contain N–C=O and P=O Functionalities: A Synthetic and Structural Study

2008

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“…Par exemple, avec le dim6thylsulfoxyde ou le diph6nylsulfoxyde, la r6action conduit aux compos6s NbOX3(RzSO)2 (Copley, Fairbrother, Grundy & Thompson, 1964) (Copley, Fairbrother & Thompson, 1965) ont pu &re pr6par6s avec l'oxyde de triph6nylphosphine et l'oxyde de triph6nyl-arsine. Des compos6s identiques (NbOCIaL2) peuvent ~tre obtenus directement 5' partir de l'oxytrichlorure de niobium: L 6tant la di6thylaniline ou la 2-m6thyl-quinoline (Leshchenko, Panyushkin, Garnovskii & Osipov, 1966).…”

Section: Introductionunclassified

Etude cristallographique du diacétonitriletrichloromonooxoniobium(V)

Chavant¹,

Daran²,

Jeannin³

et al. 1975

Acta Crystallogr Sect B

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(Recu le 9 janvier 1975(Recu le 9 janvier , acceptd le 5 fdvrier 1975 Diacetonitriletrichloromonooxoniobium crystallizes in the space group P1 with Z = 2; lattice constants are a= 5.93 + 0-03, b=7-28 +0.03, c= 11.89+0.05/~; ~= 85-4+0"3, fl= 89.3 + 0.3, 9,=99"1 +0"3 °. Intensity data were recorded with a manual four-circle diffractometer using Mo Ks radiation. The structure has been solved by the heavy-atom method and refined by full-matrix least-squares methods to a final R=0.048 based on 1137 non-zero independent reflexions. The asymmetric unit contains a niobium atom octahedrally surrounded by one oxygen, three chlorine and two nitrogen atoms. Both acetonitrile molecules are not equivalent since niobium-nitrogen bond lengths are equal to 2"245 (9) and 2.44 (2)/~. This feature is discussed in terms of valence-shell electron-pair repulsion.

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“…Thus, Fairbrother et at. (10) found that the reaction of NbCI, with an excess of Ph,PO leads to the formation of NbOCl,.-2Ph3P0 and probably Ph,PCl,, although the latter was not isolable. Other workers (8, 9, 11) report similar results although with TaCl,, only the 1 : 1 complex, TaCl,.Ph,PO was observed (8,11 produced only a trace ((2%) of NbOCl,.TPPO.…”

Section: Resultsmentioning

confidence: 98%

Reactions of 1,2,5-Triphenylphosphole and its Oxide, Sulfide, and Selenide with some Transition Metal Halides

Budd¹,

Chuchman²,

Holah³

et al. 1972

Can. J. Chem.

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Reactions of 1,2,5-triphenylphosphole (TPP) and 1,2,5-triphenylphosphole oxide (TPPO), sulfide (TPPS), and selenide (TPPSe) with some transition metal halides have been studied in dry, oxygen-free organic solvents. The reactivity of these ligands is clearly a function of the oxidation states of the metal, with the order beingFor example the ligands do not react with the metal(I1) halides (Mn, Fe, Ni), while rapid reactions occur with niobium(V) and tantalum(V). Iron(ll1) and copper(I1) are both reduced by TPP. The complexes resulting from these studies are mostly simple adducts of the various metal halides, although other species such as phospholium salts [TPPH+:I [MCI;] and oxytrichloride adducts, MOX,.TPPO (M = Nb, Ta) are also described. In the phospholium salts, the phosphole ring is protonated at the phosphorus atom which is in direct contrast to pyrrole derivatives. The origin of the oxygen atom in the oxytrichloride complexes is discussed and compared with data on the analogous triphenylphosphine oxide systems, where cleavage of the P=O bond occurs.

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The reactions of niobium and tantalum pentachlorides with triphenylphosphine and triphenylarsine oxides

Cited by 41 publications

References 16 publications

Complexes of Niobium(V) and Tantalum(V) Halides with Ligands that Contain N–C=O and P=O Functionalities: A Synthetic and Structural Study

Complexes of Niobium(V) and Tantalum(V) Halides with Ligands that Contain N–C=O and P=O Functionalities: A Synthetic and Structural Study

Etude cristallographique du diacétonitriletrichloromonooxoniobium(V)

Reactions of 1,2,5-Triphenylphosphole and its Oxide, Sulfide, and Selenide with some Transition Metal Halides

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