1,2,3,5-Diselenadiazolyls as building blocks for molecular metals. Preparation and structures of [PhCN2Se2]+PF6- and [PhCN2Se2]2

Belluz, Paul Del Bel; Cordes, A. W.; Kristof, Eva; Kristof, Peter V.; Liblong, S. W.; Oakley, Richard T.

doi:10.1021/ja00208a047

Cited by 77 publications

(41 citation statements)

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“…Preparation of 2a-g 2a was prepared by the published procedure (16,17). The IR spectrum agreed with that reported previously (18).…”

Section: Methodssupporting

confidence: 77%

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Aryl 1,5-dithia-2,4,6,8-tetrazocines. A synthetic, electrochemical, and structural investigation

Boeré¹,

Moock²,

Derrick³

et al. 1993

Can. J. Chem.

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New preparative routes to the title compounds are reported in which the yields are substantially improved over previous methods. In one method, reaction of O2 with a mixture of XC6H,CN2S2+~1-and Ph,Sb leads to the products in 40-60% yield. In another, the reaction of the same salts with silylated amidines XC6H4C{NSiMe3}N(SiMe3)2 in a 1 : 1 mol ratio leads to the same compounds in 18-65% yield. The syntheses of 3,7-(XC6H,)2{CN2S2N,C), X = H, 4-CH,, 4-CH,O, 4 4 , 4-CF,, and 3-CF,, are reported. Mixed derivatives were also prepared, but not isolated as pure compounds. The crystal structure of the 4-CF, compound has been determined by X-ray diffraction; triclinic, with Z = 1; cell dimensions: a = 6.835(2), b = 9.936(3), c = 6.320(2) A , a = 96.44(3)", P = 102.88(3)", y = 88.42(3)". R = 3.4%, R,,. = 3.5% for 1100 data. The eight-membered ring is flat with equivalent bond lengths between any two types of atoms, indicative of a delocalized electron distribution. ' The 10a central aromatic rings have been oxidized and reduced in CHzC1, using voltammetric methods. The reversible one-electron reduction step gives stable 1 l n species. On a dCveloppC de nouvelles voies de synthkse des compos6s mentionnes dans le titre qui donnent des rendements de beaucoup superieurs 2 ceux rapportes anterieurement. Dans une mCthode, la rCaction du O2 avec un melange de HC6H4CN2S2+C1-et de Ph3Sb conduit aux produits avec des rendements allant de 40 a 60%. Dans une autre mCthode, la reaction des mCmes sels avec les amidines silylkes XC6H,C{NSiMe,}N(SiMe,),, dans un rapport molaire de 1 : 1, conduit aux mCmes produits avec des rendements allant de 18 a 65%. Donc on rapporte la synthkse des 3,7-(XC6H,)2{CN2S2N2C), X = H, 4-CH,, 4-CH,O, 4-C1, 4-CF3 et 3-CF3. On a aussi prepare des derives mixtes; toutefois, il n'a pas Cte possible de les isqler 2 I'Ctat pur. On a determine la structure cristallin: du compose 4-CF, par diffraction des rayons X; triclinique, P l , avec a = 8,835(2), b = 9,936(3) et c = 6,320(2) A , a = 96,44(3)", P = 102,88(3)" et y = 88,42(3)", Z = 1. R = 3,4% et R,, = 3.5% pour I100 donnCes. Le cycle a huit chainons est plat alors que les longueurs des liaisons sont Cquivalentes entre tous les atomes pris deux a deux; ce resultat indique que la distribution Clectronique est dClocalisCe. Utilisant des methodes voltampCrometriques et operant dans le CH2C1,, on a oxydC et reduit les cycles aromatiques 2 10 Clectrons a . La reduction reversible par un electron conduit a des espkces stables a 11 electrons n . En accord avec les etudes chimiques anterieures, les composCs mentionnes dans le titre sont beaucoup plus difficiles a oxyger que le 3,7-[(CH3)2Nl2{CNzSzNzC}.[Traduit par la redaction]

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“…Preparation of 2a-g 2a was prepared by the published procedure (16,17). The IR spectrum agreed with that reported previously (18).…”

Section: Methodssupporting

confidence: 77%

“…The preparation of salts 2 and radicals 3 follows a wellestablished route (16,17). We found that the best solvent for the preparation of the rather insoluble chloride salts 2 is indeed acetonitrile.…”

Section: Synthetic Methodsmentioning

confidence: 97%

Aryl 1,5-dithia-2,4,6,8-tetrazocines. A synthetic, electrochemical, and structural investigation

Boeré¹,

Moock²,

Derrick³

et al. 1993

Can. J. Chem.

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“…92,134 Studies on diselenadiazolyl radicals 45 are more limited compared to their sulfur counterparts 35 owing, in part, to the lower solubility and thermal stability of the former. The few EPR spectra which have been reported 86,134 consist of a broad featureless singlet; g-values for 45 are consistently higher than for the sulfur analogues 35, as anticipated for radicals with substantial spin density on selenium. Computational and experimental studies on the prototypical diselenadiazolyl radical (R = H) point to an electronic structure analogous to that for the corresponding sulfur-based radical.…”

Section: 235-diselenadiazolylsmentioning

confidence: 58%

“…83 A more recent use of S 3 N 3 Cl 3 in the synthesis of dithiadiazolium chlorides involves the cycloaddition reaction of the NSCl monomer (obtained by heating S 3 N 3 Cl 3 ) with in situ generated nitrile sulfides. 84 produces dithiadiazolium chlorides in low yields 85 ; the use of N,N,N -tris(trimethylsilyl) derivatives, 86 or N -lithio-N ,N -bis(trimethylsilyl)amidines 87 improves yields significantly and permits the synthesis of selenium analogues (Section 9.3.2.1). Other routes have been reported but tend to be substrate-specific (for example Mews has developed routes to the 4-halogeno-1,2,3,5-dithiadiazolium cations starting from N,Nbis(trimethylsilyl)carbodiimide).…”

Section: 235-dithiadiazolyl Radicalsmentioning

confidence: 99%

“…86 These radicals are made by reduction (triphenylantimony) of the corresponding 1,2,3,5-diselenadiazolium cations 44, which are in turn prepared exclusively from the reaction of silylated amidines (either N,N,N -tris(trimethylsilyl) 86 or N -lithio-N ,N -bis(trimethylsilyl) 92 ) with selenium dichloride (SeCl 2 ) (Scheme 9.12). The selenium dichloride is generated in situ from selenium tetrachloride (SeCl 4 ) and a reducing agent, either triphenylantimony 86,123,126 or elemental selenium. 92,134 Studies on diselenadiazolyl radicals 45 are more limited compared to their sulfur counterparts 35 owing, in part, to the lower solubility and thermal stability of the former.…”

Section: 235-diselenadiazolylsmentioning

confidence: 99%

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The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials

Hicks

2010

Stable Radicals

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Synthesis and Chemistry of Dithiadiazole Free Radicals [4-(4′-C5H4N)CN2S2] and [4-(3′-C5H4N)CN2S2]; X-ray Crystal Structures of [Pd3{μ-SNC(Ar′)NS–S,S′}2(PPh3)4] (Ar′ = 4′-C5H4N, 4′-C5H4NBEt3 and 3′-C5H4NBEt3)

Wong¹,

Sun²,

Wong³

et al. 2000

Eur. J. Inorg. Chem.

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Two new 1,2,3,5‐dithiadiazoles, [4‐(4′‐C5H4N)CN2S2] (L1) and [4‐(3′‐C5H4N)CN2S2] (L2), with different pyridyl groups at the 4‐position were prepared. As Lewis bases, the dithiadiazoles reacted with Lewis acids via their pyridyl groups to form acid‐base adducts with retention of the five‐membered dithiadiazole ring. Ligands L1 and L2 reacted with excess triethylborane to give L1BEt3 and L2BEt3 (1a and 1b) and with Mn(CO)5Br to give the fac‐Mn(CO)3Br(L1)2 (2a) and fac‐Mn(CO)3Br(L2)2 (2b) complexes. When reacted with Pd0 complexes, namely, Pd(PPh3)4 and a mixture of [Pd2(dba)3] and dppf, the dithiadiazoles underwent ring‐opening reaction by reductive cleavage of the S–S bond of the dithiadiazole ring. The resulting formation of Pd–S bonds gave the corresponding trinuclear complexes [Pd3{μ‐SNC(4′‐C5H4N)NS‐S,S′}2(PPh3)4] (3a), [Pd3{μ‐SNC(3′‐C5H4N)NS‐S,S′}2(PPh3)4] (3b), and [Pd3{μ‐SNC(4′‐C5H4N)NS‐S,S′}2(dppf)2] (4) [dba = dibenzylideneacetone, dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene]. Complexes 3a and 3b reacted with excess triethylborane to give the corresponding acid‐base adducts [Pd3{μ‐SNC(4′‐C5H4NBEt3)NS‐S,S′}2(PPh3)4] (5a) and [Pd3{μ‐SNC(3′‐C5H4NBEt3)NS‐S,S′}2(PPh3)4] (5b.) Complex 3a reacted with Mn(CO)5Br to give {[Pd3{μ‐SNC(4′‐C5H4N)NS‐S,S′}2(PPh3)4][MnBr(CO)3]}n (6). The structures of 3a, 5a, and 5b were established by X‐ray crystallography.

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1,2,3,5-Diselenadiazolyls as building blocks for molecular metals. Preparation and structures of [PhCN2Se2]+PF6- and [PhCN2Se2]2

Cited by 77 publications

References 2 publications

Aryl 1,5-dithia-2,4,6,8-tetrazocines. A synthetic, electrochemical, and structural investigation

Aryl 1,5-dithia-2,4,6,8-tetrazocines. A synthetic, electrochemical, and structural investigation

The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials

Synthesis and Chemistry of Dithiadiazole Free Radicals [4-(4′-C5H4N)CN2S2] and [4-(3′-C5H4N)CN2S2]; X-ray Crystal Structures of [Pd3{μ-SNC(Ar′)NS–S,S′}2(PPh3)4] (Ar′ = 4′-C5H4N, 4′-C5H4NBEt3 and 3′-C5H4NBEt3)

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