Preparation and crystal structure of S2I42+(AsF6–)2containing the distorted right triangular prismatic disulphur tetraiodine(2+) cation and a disulphur unit of bond order greater than two

Passmore, Jack; Sutherland, George; Whidden, Thomas K.; White, Peter S.

doi:10.1039/c39800000289

Cited by 32 publications

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“…Anstelle des zweiten besetzten s-"lone-pair"-Orbitals gibt es im 1M das Ge-Ge-bindende p ? [22][23][24] Man beachte, dass 1M als hypoelektronisch angesehen werden kann (12 Valenzelektronen für den Ge 2 Ga 2 -Ring) während die Si 2 (NAr) 2 -Referenzverbindung 16 Valenzelektronen für den Si 2 N 2 -Ring aufweist.…”

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Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

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Viel π und kein σ! Im Ga2Ge2‐Kern von Ge2[Ga(DPP)]2 liegt einer ausführlichen theroretischen Analyse zufolge zwischen den beiden Ge‐Atomen keine σ‐Bindung vor, eine transannulare π‐Bindung hingegen schon (siehe Bild). Die Verbindung entsteht bei der Reduktion von (PCy)3⋅GeCl2 mit Ga(DDP)/KC8, die als ein weiteres Produkt auch Ge4[Ga(DPP)]2 mit einem Ge4‐Tetraeder liefert. DDP = HC(CMeNC6H3‐2,6‐iPr2)2.

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“…Uns ist kein anderes Beispiel bekannt, in dem ein Molekül eine p-Bindung zwischen zwei Atomen ohne eine s-Bindung aufweist. [22][23][24] Eingegangen am 7. Juni 2012, veränderte Fassung am 15.…”

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Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

et al. 2012

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“…The estimated bond distaaces and angles for SBr3+, %I3+, and Te13+ deviated (-0.02 A and lo) from the values obtained in the present work and for Te13+ in Te13AsF6 (13).3 A more accurate fit is desirable, and in addition the method cannot give an accurate estimate of the S-I distance in S13MfF6, as the method relies on the structural determination of the isoelectronic Group V trihalide (PI3) in the gas phase, for which an accurate structure is not available 2Various attempts to prepare solid S13M1F6 in our laboratory led in all cases to S214(MF6)2 + I2 solids (19,51). (P-I distance in P13(g) = 2.43(3) A (50)).…”

Section: Cation-anion Interactionsmentioning

confidence: 99%

The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆

Johnson¹,

Murchie²,

Passmore³

et al. 1987

Can. J. Chem.

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Te13SbF6 (4) are reported and the quantitative preparation of the hitherto unknown 3 and 4 from SbF5 and the respectiye elements in SO2 are given. Crystal data are asfollows: 1, monoclinic, spacegroup P21/c, with a = 8.015(1) A, b = 9.342(1)A, c = 12.126(2), P = 97.81(1)", andZ = 4; 2, monoclinic, space group P21/c, with a = 8.380(2) 4, b = 10.237(1) 4, c = 12.524(1) A, P = 99.36(1)", and Z = 4; 3, monoclinic, space group P 2 , / c , with ci = 8.548(2) A, b = 10.297(6) A, c = 12.877(8) 6, P = 98.70(3)", and Z = 4; 4, monoclinic, space group P21/c, with a = 8.463(1) A, b = 10.676(2) A, c = 13.121(4) A, P = 100.05(1), and Z = 4.Compounds l , 2 , 3 , and 4 are isostructural and were refined to a final R values of 0.040,0.05 1,0.047, and 0.037, respectively. The structures of these salts consist of essentially discrete MX3+ cations and M1F6-anions (M = S, Se, Te; X = Br, I; M' = As, Sb) with some cation-anion interactions. The Se13+ bond distances and angles were essentially identical in both AsF6-and SbF6-salts (average Se-I distance and I-Se-I angle for AsF6-salt; 2.508(2) A, 102.4(1)" and for SbF6_ salt; 2.512(1) A, 102.3(1)"). Similarly the average Te-I bond distance and I-Te-I angle for Te13SbF6 were 2.666(1) A and 99.8(1)" which are essentially identical to those in the previously reported Te13AsF6. The average S-Br distance and Br-S-Br angle were 2.142(6) A and 103.4(2)" in SBr3AsF6. Estimates of the S-I bond distance and I-S-I bond angle in the as yet unknown S13M1F6 are made from the extrapolation of MX3+ data. The bond distances observed in the simple MX3+ cations (M = S, Se, Te; X = C1, Br, I) with anions of very low basicity are within 0.02 A of the corresponding distances calculated by the Schomaker-Stevenson equation. The observed and estimated bond distances in SBr3+, S13+, and Se13+ are significantly longer than the corresponding S-Br, S-I, and Se-I distances in S71+, S7Br+, and Se6II2+. This observation is used to support the thesis that the long intra-cationic halogen-chalcogen contacts in polychalcogen-halogen cations are weakly bonding, and responsible for the cluster-like nature of these cations. The heats of formation of 1 and 2 from their respective elements and AsF5 were estimated. On utilise cetteobservation pour supporter la thkse selon laquelle les contacts intra-ioniques halogknes-chalcog&nes, qui sont longs dans les cations polychalcogknes-halogknes, provoquent une liaisons faible qui est responsable du fait que ces cations sont pratiquement des agrkgats. On a tvaluk les chaleurs de formation des composks I et 2 h partir du AsFs et de leurs ClCments respectifs.[Traduit par la revue]

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“…We have recently prepared and determined the crystal structures of the sulphur iodine cations S71MF6 (M = As, Sb) (1 -3), [(S7I)21][SbF6]3'2AsF3 (4,5 ) , (S~I)&(ASF~)~ (4, 61, and S214(A~F6)2 (7). It was of interest to determine whether iodine was unique in its ability to form cations of this sort, therefore, we explored the analogous sulphur-bromine system, and the results are reported in detail below.…”

Section: Introductionmentioning

confidence: 99%

The preparation of S₇BrMF₆ (M = As, Sb), and the preparation and crystal structure of (S₇Br)₄S₄(AsF₆)₆ containing the bromo-cycloheptasulphur (1+) cation

Passmore¹,

Sutherland²,

Whidden³

et al. 1985

Can. J. Chem.

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. S7BrMFh (M = As, Sb) were prepared essentially quantitatively by a variety of similar routes to those that led to S71MF6; and in addition, by the reaction of bromine and S71AsFh. (S,Br),S,(AsF,), was prepared essentially quantitatively directly from sulphur, bromine, and arsenic pentafluoride in the appropriate ~a t i o s . Crystals of (S7Br)4S4(AsFh)6 are isostructural with (S71)4S4(A~F6)6r space group P4/11, a = 19.19(3), c = 8.01(1) A. The structure was refined from a low temperature set of data to a final R = 0.12. The salt contains a discrete planar S4" and bromo-cycloheptasulphur ( I +) cations, the latter having a similar geometry, sulphur-sulphur bond distances and an intra-cationic halogen-sulphur contact to that observed in S71+.JACK PASSMORE, GEORGE SUTHERLAND, TOM K. WHIDDEN, PETER S. WHITE et CHI-MING WONG. Can. J. Chem. 63, 1209Chem. 63, (1985.Utilisant diverses methodes semblables B celles qui ont permis de prCparer le S71MF6, on a prCpar6 le S7BrMFh (M = As, Sb) avec un rendement pratiquement quantitatif; on ['a aussi obtenu par la reaction du brome et du S71AsFh. Par reaction du soufre, du brome et du pentafluorure d'arsenic dans des proportions appropries, on a prepare le (S7Br),S4(AsF,), avec un rendement essentiellement quantitatif. . It was of interest to determine whether iodine was unique in its ability to form cations of this sort, therefore, we explored the analogous sulphur-bromine system, and the results are reported in detail below. A preliminary communication briefly mentioned (s7Br).,S4(AsF6) (6). Prior to this work the known binary sulphur-bromine species were S,Br2 (x = 2 to ca. 10) (of which only S2Br2 is stable) (8), SBr3MF6 (M = As, Sb) (9) salts, and the rather unstable NH,SBr (8).

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Preparation and crystal structure of S₂I₄²⁺(AsF₆^–)₂containing the distorted right triangular prismatic disulphur tetraiodine(2+) cation and a disulphur unit of bond order greater than two

Cited by 32 publications

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Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆

The preparation of S₇BrMF₆ (M = As, Sb), and the preparation and crystal structure of (S₇Br)₄S₄(AsF₆)₆ containing the bromo-cycloheptasulphur (1+) cation

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Preparation and crystal structure of S2I42+(AsF6–)2containing the distorted right triangular prismatic disulphur tetraiodine(2+) cation and a disulphur unit of bond order greater than two

Cited by 32 publications

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Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge2‐ und Ge4‐Spezies

Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge2‐ und Ge4‐Spezies

The preparation of SeI3SbF6 and TeI3SbF6; the X-ray crystal structures of SBr3AsF6, SeI3AsF6, SeI3SbF6, and TeI3SbF6; some considerations of the energetics of the formation of SBr3AsF6 and SeI3AsF6

The preparation of S7BrMF6 (M = As, Sb), and the preparation and crystal structure of (S7Br)4S4(AsF6)6 containing the bromo-cycloheptasulphur (1+) cation

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Preparation and crystal structure of S₂I₄²⁺(AsF₆^–)₂containing the distorted right triangular prismatic disulphur tetraiodine(2+) cation and a disulphur unit of bond order greater than two

Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

Mit N‐heterocyclischem Gallylen stabilisierte niedervalente Ge₂‐ und Ge₄‐Spezies

The preparation of SeI₃SbF₆ and TeI₃SbF₆; the X-ray crystal structures of SBr₃AsF₆, SeI₃AsF₆, SeI₃SbF₆, and TeI₃SbF₆; some considerations of the energetics of the formation of SBr₃AsF₆ and SeI₃AsF₆

The preparation of S₇BrMF₆ (M = As, Sb), and the preparation and crystal structure of (S₇Br)₄S₄(AsF₆)₆ containing the bromo-cycloheptasulphur (1+) cation