S. Ivanov, Michael A. Kozee, W. A. Merrill, S. Agarwal, L. F. Dahl
{"title":"Cyclo-[Ni(μ2-SPh)2]9和Cyclo-[Ni(μ2-SPh)2] 11:含有几何上前所未有的9元和11元环体系的新型低聚环型镍(II)硫代酸盐","authors":"S. Ivanov, Michael A. Kozee, W. A. Merrill, S. Agarwal, L. F. Dahl","doi":"10.1039/B204273H","DOIUrl":null,"url":null,"abstract":"Two new oligomeric types of toroidal nickel(II) monothiolate ring systems, cyclo-[Ni(SPh)2]11 \n(1) and cyclo-[Ni(SPh)2]9 \n(2), containing heretofore unknown 11-membered (n \n= 11) and 9-membered (n \n= 9) ring-geometries, respectively, are reported. Our initial isolation of 1 was as an unexpected by-product that resulted from unsuccessful attempts to produce crystalline nanostructural gold thiolate clusters from reactions of alkyl/phenyl thiols with the recently prepared nanostructural [Au16Ni24(CO)40]4− cluster. The unique architecture of 1 led to a designed preparation of it by a direct synthetic route involving reactions of PhSNa with Ni(ClO4)2 in THF or DMF. Slow addition of the reactants at low temperature afforded two crystal forms of 1: namely, the previously isolated triclinic crystals (P) as well as solvated monoclinic crystals (C2/c) \n(1a). Normal mixing of the reactants at room temperature gave rise to a trigonal crystal form (P12/c) that was determined to be cyclo-[Ni(SPh)2]9 \n(2). The atomic arrangements and stoichiometries of both 1 and 2 were unequivocally established from low-temperature CCD area-detector X-ray diffractometry studies; particularly noteworthy is that the structures of both crystal forms of 1 possess nearly identical molecular geometries (including the phenyl-ring orientations) along with an encapsulated THF molecule. These new air-stable molecular additions to the cyclo-[Ni(μ2-SR)2]n family (with n \n= 4, 5, 6, and 8) are of particular stereochemical interest in that: (1) in sharp contrast to the previously known monodentate thiolate-bridged members which ideally possess regular convex Ni–S toroids, the assembled n-localized edge-fused square-planar [NiS4] subunits found in the triclinic and monoclinic crystal forms of undecanickel 1 and in the trigonal crystal form of nonanickel 2 have irregularly-shaped mixed concave/convex toroidal pseudo-C2v and pseudo-D3h ring geometries, respectively, that are geometrically unique; (2) \n1 is the first host member of any known cyclo-[Ni(SR)2]n oligomer to have a co-crystallized solvated guest molecule (viz., THF); and (3) the observed orientations of adjacent phenyl rings attached to the highly pyramidal sulfur atoms in both 1 and 2 suggest the occurrence of weakly attractive pairwise phenyl⋯phenyl dispersion forces that are presumed to stabilize these novel nickel(II) phenylthiolate oligomers. A comparative analysis of the salient solid-state structural features of the idealized Ni–S ring geometries of the resulting entire cyclo-[Ni(SPh)2]n family (n \n= 4, 5, 6, 8, 9, and 11) is presented (under the assumed absence of sterically crowded R-substituents and/or abnormal packing effects). The unsymmetrical enlargement of the pseudo-threefold 9-membered ring in 2 by the formal insertion of two adjacent [Ni(SPh)2] units to give an otherwise analogous Ni–S framework of the 11-membered ring in 1 is attributed to the elongated template-geometry of the guest molecule coupled with the maintenance of attractive pairwise phenyl ring interactions.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":"3 1","pages":"4105-4115"},"PeriodicalIF":0.0000,"publicationDate":"2002-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"42","resultStr":"{\"title\":\"Cyclo-[Ni(μ2-SPh)2]9 and cyclo-[Ni(μ2-SPh)2]11: new oligomeric types of toroidal nickel(II) thiolates containing geometrically unprecedented 9- and 11-membered ring systems\",\"authors\":\"S. Ivanov, Michael A. Kozee, W. A. Merrill, S. Agarwal, L. F. Dahl\",\"doi\":\"10.1039/B204273H\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Two new oligomeric types of toroidal nickel(II) monothiolate ring systems, cyclo-[Ni(SPh)2]11 \\n(1) and cyclo-[Ni(SPh)2]9 \\n(2), containing heretofore unknown 11-membered (n \\n= 11) and 9-membered (n \\n= 9) ring-geometries, respectively, are reported. Our initial isolation of 1 was as an unexpected by-product that resulted from unsuccessful attempts to produce crystalline nanostructural gold thiolate clusters from reactions of alkyl/phenyl thiols with the recently prepared nanostructural [Au16Ni24(CO)40]4− cluster. The unique architecture of 1 led to a designed preparation of it by a direct synthetic route involving reactions of PhSNa with Ni(ClO4)2 in THF or DMF. Slow addition of the reactants at low temperature afforded two crystal forms of 1: namely, the previously isolated triclinic crystals (P) as well as solvated monoclinic crystals (C2/c) \\n(1a). Normal mixing of the reactants at room temperature gave rise to a trigonal crystal form (P12/c) that was determined to be cyclo-[Ni(SPh)2]9 \\n(2). The atomic arrangements and stoichiometries of both 1 and 2 were unequivocally established from low-temperature CCD area-detector X-ray diffractometry studies; particularly noteworthy is that the structures of both crystal forms of 1 possess nearly identical molecular geometries (including the phenyl-ring orientations) along with an encapsulated THF molecule. These new air-stable molecular additions to the cyclo-[Ni(μ2-SR)2]n family (with n \\n= 4, 5, 6, and 8) are of particular stereochemical interest in that: (1) in sharp contrast to the previously known monodentate thiolate-bridged members which ideally possess regular convex Ni–S toroids, the assembled n-localized edge-fused square-planar [NiS4] subunits found in the triclinic and monoclinic crystal forms of undecanickel 1 and in the trigonal crystal form of nonanickel 2 have irregularly-shaped mixed concave/convex toroidal pseudo-C2v and pseudo-D3h ring geometries, respectively, that are geometrically unique; (2) \\n1 is the first host member of any known cyclo-[Ni(SR)2]n oligomer to have a co-crystallized solvated guest molecule (viz., THF); and (3) the observed orientations of adjacent phenyl rings attached to the highly pyramidal sulfur atoms in both 1 and 2 suggest the occurrence of weakly attractive pairwise phenyl⋯phenyl dispersion forces that are presumed to stabilize these novel nickel(II) phenylthiolate oligomers. A comparative analysis of the salient solid-state structural features of the idealized Ni–S ring geometries of the resulting entire cyclo-[Ni(SPh)2]n family (n \\n= 4, 5, 6, 8, 9, and 11) is presented (under the assumed absence of sterically crowded R-substituents and/or abnormal packing effects). The unsymmetrical enlargement of the pseudo-threefold 9-membered ring in 2 by the formal insertion of two adjacent [Ni(SPh)2] units to give an otherwise analogous Ni–S framework of the 11-membered ring in 1 is attributed to the elongated template-geometry of the guest molecule coupled with the maintenance of attractive pairwise phenyl ring interactions.\",\"PeriodicalId\":17317,\"journal\":{\"name\":\"Journal of The Chemical Society-dalton Transactions\",\"volume\":\"3 1\",\"pages\":\"4105-4115\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2002-11-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"42\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of The Chemical Society-dalton Transactions\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/B204273H\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society-dalton Transactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/B204273H","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Cyclo-[Ni(μ2-SPh)2]9 and cyclo-[Ni(μ2-SPh)2]11: new oligomeric types of toroidal nickel(II) thiolates containing geometrically unprecedented 9- and 11-membered ring systems
Two new oligomeric types of toroidal nickel(II) monothiolate ring systems, cyclo-[Ni(SPh)2]11
(1) and cyclo-[Ni(SPh)2]9
(2), containing heretofore unknown 11-membered (n
= 11) and 9-membered (n
= 9) ring-geometries, respectively, are reported. Our initial isolation of 1 was as an unexpected by-product that resulted from unsuccessful attempts to produce crystalline nanostructural gold thiolate clusters from reactions of alkyl/phenyl thiols with the recently prepared nanostructural [Au16Ni24(CO)40]4− cluster. The unique architecture of 1 led to a designed preparation of it by a direct synthetic route involving reactions of PhSNa with Ni(ClO4)2 in THF or DMF. Slow addition of the reactants at low temperature afforded two crystal forms of 1: namely, the previously isolated triclinic crystals (P) as well as solvated monoclinic crystals (C2/c)
(1a). Normal mixing of the reactants at room temperature gave rise to a trigonal crystal form (P12/c) that was determined to be cyclo-[Ni(SPh)2]9
(2). The atomic arrangements and stoichiometries of both 1 and 2 were unequivocally established from low-temperature CCD area-detector X-ray diffractometry studies; particularly noteworthy is that the structures of both crystal forms of 1 possess nearly identical molecular geometries (including the phenyl-ring orientations) along with an encapsulated THF molecule. These new air-stable molecular additions to the cyclo-[Ni(μ2-SR)2]n family (with n
= 4, 5, 6, and 8) are of particular stereochemical interest in that: (1) in sharp contrast to the previously known monodentate thiolate-bridged members which ideally possess regular convex Ni–S toroids, the assembled n-localized edge-fused square-planar [NiS4] subunits found in the triclinic and monoclinic crystal forms of undecanickel 1 and in the trigonal crystal form of nonanickel 2 have irregularly-shaped mixed concave/convex toroidal pseudo-C2v and pseudo-D3h ring geometries, respectively, that are geometrically unique; (2)
1 is the first host member of any known cyclo-[Ni(SR)2]n oligomer to have a co-crystallized solvated guest molecule (viz., THF); and (3) the observed orientations of adjacent phenyl rings attached to the highly pyramidal sulfur atoms in both 1 and 2 suggest the occurrence of weakly attractive pairwise phenyl⋯phenyl dispersion forces that are presumed to stabilize these novel nickel(II) phenylthiolate oligomers. A comparative analysis of the salient solid-state structural features of the idealized Ni–S ring geometries of the resulting entire cyclo-[Ni(SPh)2]n family (n
= 4, 5, 6, 8, 9, and 11) is presented (under the assumed absence of sterically crowded R-substituents and/or abnormal packing effects). The unsymmetrical enlargement of the pseudo-threefold 9-membered ring in 2 by the formal insertion of two adjacent [Ni(SPh)2] units to give an otherwise analogous Ni–S framework of the 11-membered ring in 1 is attributed to the elongated template-geometry of the guest molecule coupled with the maintenance of attractive pairwise phenyl ring interactions.