Synthesis and characterization of bis[tetraphenylphosphonium] hexaselenoxoditungstate(2-)

Lü, Ying; Ansari, Mohammad A.; Ibers, James A.

doi:10.1021/ic00320a023

Cited by 25 publications

(8 citation statements)

References 2 publications

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“…The structures of the Sn 2 Ch 6 4- anions (Ch = Se, Te) are based on two edge-sharing distorted SnCh 4 tetrahedra and are therefore isostructural with B 2 H 6 , W 2 Se 6 2- , and Ge 2 Ch 6 4- (Ch = S, Se,). The two distinct Sn−Ch bond distances, i.e., Sn−Ch t and Sn−Ch mb , are slightly shorter and longer, respectively, than those found in the crystal structures of SnCh 4 4- [Se, 2.494(1)−2.536(1) Å; Te, 2.710(3)−2.819(2) Å 30 ].…”

Section: Resultsmentioning

confidence: 99%

Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)

et al. 1996

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The seleno- and tellurostannate(IV) anions Sn2Ch6 4- and Sn2Ch7 4- (Ch = Se, Te) have been obtained by extraction of the ternary alloys KSn0.67Se1.93 and KSn0.63Te1.70 in ethylenediamine (en) and/or liquid NH3 in the absence and in the presence of nonstoichiometric amounts of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) with respect to K+. The anions were characterized in solution for the first time by natural abundance 77Se, 119Sn, and 125Te NMR spectroscopy. The magnitudes of the relativistically corrected reduced coupling constants 1 K(Sn−Cht)RC, 1 K(Sn−Chmb)RC, and 1 K(Sn−Chdb)RC were shown to be consistent with a significant degree of s-character in the bonding. The Sn−Chmb and Sn−Cht bond distances observed for the dimeric SnCh3 2- anions, namely Sn2Ch6 4-, in K+(N(CH3)4 +)3Sn2Se6 4- (1), (enH+)2(2,2,2-crypt-K+)2Sn2Se6 4- (2), and (K+)2(2,2,2-crypt-K+)2Sn2Te6 4- (3) were shown to correlate with the 1 K(Sn−Ch)RC values, indicating that the solid-state molecular structures of the anions are retained in solution. The Raman spectra of compounds 1−3 are also reported along with their respective factor-group analyses. The novel HOSnTe3 3- anion, the hydroxide derivative of the SnTe3 2- anion, has been structurally characterized by X-ray crystallography in K+(2,2,2-crypt-K+)2HOSnTe3 3- (4) and in K+(2,2,2-crypt-K+)2HOSnTe3 3-·en (5) and represents the first example of a simple mixed hydroxychalcogenide anion of tin.

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Section: Resultsmentioning

confidence: 99%

Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)

et al. 1996

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“…Some of the new clusters can undergo further chemistry leading to new binary anions by reduction of selenium-selenium bonds (Figure 15). 90 The reduction of coordinated polyselenides should be a general reaction type, although not many examples have yet been reported (eq 86).…”

Section: Groupmentioning

confidence: 99%

New developments in the coordination chemistry of inorganic selenide and telluride ligands

Roof¹,

Kolis²

1993

Chem. Rev.

378

106

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“…A family of compounds of general formula [W 2 Se 2 (l-Se) 2 (Se n ) 2 ] 2− (n = 2, 3, 4) was prepared by Ibers and co-workers in 1988 where often the presence of several isomers coexist with higher nuclearity compounds. [28][29][30] The structure of complex [2]PF 6 has been determined by single crystal X-ray diffraction. Compound [2]PF 6 crystallizes in the chiral space group P2 1 .…”

Section: Introductionmentioning

confidence: 99%

“…This arrangement is also found in the dinuclear complex (Et 4 N)[Mo 2 O 2 (l-S) 2 -(l-CF 3 CO 2 )(S 2 P(OEt) 2 ) 2 ] and other closely related complexes of general formula [Mo 2 X 2 (l-Q) 2 L 2 ] (X = O, S, Se; Q = S, Se; L = bidentate ligand). [29][30][31][32][33][34][35][36] Table 1 shows a list of selected bond lengths in compound [2]PF 6 together with those of other dinuclear complexes containing similar W 2 Q 2 (l-Se) 2 (Q = O, Se) cluster cores.…”

Section: Introductionmentioning

confidence: 99%

A combined stopped-flow, electrospray ionization mass spectrometry and³¹P NMR study on the acetic acid-mediated fragmentation of the hydroxo-chalcogenide cluster [W₃Se₄(OH)₃(dmpe)₃]⁺(dmpe = 1,2-bis(dimethylphosphanyl)ethane) to yield the dinuclear [W₂Se₂(µ-Se)₂(µ-CH₃CO₂)(dmpe)₂]⁺complex

et al. 2006

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The reaction of the incomplete-cuboidal [W(3)Se(4)(OH)(3)(dmpe)(3)](+) ([1](+)) cluster with acetic acid in acetonitrile solution leads to cluster fragmentation with formation of the dinuclear [W(2)Se(2)(mu-Se)(2)(mu-CH(3)CO(2))(dmpe)(2)](+) ([2](+)) complex. The X-ray structure of [2]PF(6) presents two equivalent metal centres bridged by one acetate ligand. Each W atom is additionally coordinated by one terminal selenium atom, two bridging selenido and two diphosphane phosphorus atoms in an essentially octahedral environment. Stopped-flow and conventional UV-vis studies indicate that fragmentation of [1](+) into [2](+) occurs through a complex mechanism. Three steps can be distinguished in the stopped-flow time scale, all of them showing a first order dependence with respect to the acetic acid concentration, followed by very slow spectral changes that lead to the formation of [2](+). Phosphorus NMR, electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) have been used to identify the nature of the reaction intermediates formed in the different steps. These studies indicate that the first two steps correspond to the formal substitutions of the hydroxo ligands at two metal centres by terminal acetate ligands. The third step involves bridging of one of the terminal acetate ligands, which actually prepares the trinuclear cluster to afford the acetate-bridged [W(2)Se(2)(mu-Se)(2)(mu-CH(3)CO(2))(dmpe)(2)](+) ([2](+)) complex. Although the precise details of the final conversion to [2](+) have not been established, the results obtained by combination of the different experimental techniques provide a complete picture of the speciation of the cluster [1](+) in acetonitrile solutions containing acetic acid.

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Synthesis and characterization of bis[tetraphenylphosphonium] hexaselenoxoditungstate(2-)

Cited by 25 publications

References 2 publications

Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)

Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)

New developments in the coordination chemistry of inorganic selenide and telluride ligands

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Synthesis and characterization of bis[tetraphenylphosphonium] hexaselenoxoditungstate(2-)

Cited by 25 publications

References 2 publications

Ditin(IV) Chalcogenide Anions: 77Se, 119Sn, and 125Te Solution NMR Study of the Sn2Ch64- and Sn2Ch74- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K+(N(CH3)4+)3Sn2Se64-, (enH+)2(2,2,2-crypt-K+)2Sn2Se64-, and (K+)

Ditin(IV) Chalcogenide Anions: 77Se, 119Sn, and 125Te Solution NMR Study of the Sn2Ch64- and Sn2Ch74- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K+(N(CH3)4+)3Sn2Se64-, (enH+)2(2,2,2-crypt-K+)2Sn2Se64-, and (K+)

New developments in the coordination chemistry of inorganic selenide and telluride ligands

A combined stopped-flow, electrospray ionization mass spectrometry and31P NMR study on the acetic acid-mediated fragmentation of the hydroxo-chalcogenide cluster [W3Se4(OH)3(dmpe)3]+(dmpe = 1,2-bis(dimethylphosphanyl)ethane) to yield the dinuclear [W2Se2(µ-Se)2(µ-CH3CO2)(dmpe)2]+complex

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Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)

Ditin(IV) Chalcogenide Anions: ⁷⁷Se, ¹¹⁹Sn, and ¹²⁵Te Solution NMR Study of the Sn₂Ch₆^4- and Sn₂Ch₇^4- (Ch = Se, Te) Anions, X-ray Crystal Structures and Raman Spectra of K⁺(N(CH₃)₄⁺)₃Sn₂Se₆^4-, (enH⁺)₂(2,2,2-crypt-K⁺)₂Sn₂Se₆^4-, and (K⁺)