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Jochen Münchenberg Jens R. Goerlich Axel K. Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(2):348-354
Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 · Et2O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond. 相似文献
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合成了3种化合物 [2-ClPyH]2CoCl4(1), [2-ClPyH]2NiCl4(2)和[2-ClPyH]2CuCl4(3), 单晶X射线衍射法晶体结构测定结果表明, 这3种化合物是同形加合物, 在它们的结构中, [2-ClPyH]+离子呈平面状, 而[MCl4]2-离子为变形的四面体. 晶体结构分析发现晶体中存在N—H…Cl和C—H…Cl氢键, 以及Cl…Cl分子间相互作用和π-π堆积作用. 对自由状态下独立的配位离子进行的几何构型优化, 以及三维周期性条件下几何结构优化的量子化学计算结果表明, 标题化合物中具有方向性和选择性的氢键决定延伸性结构的方向, 而相对较弱的卤素…卤素作用在最终晶体结构的确定中扮演很重要的角色. 相似文献
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Mitsushiro Nomura Chikako Fujita-Takayama 《Journal of organometallic chemistry》2011,696(25):4018-4038
This review paper summarizes the reactivities of metal dithiolene complexes based on the ‘coexistence of aromaticity and unsaturation’ in the five-membered metallacycle, the so-called metalladithiolene ring (MS2C2). The 16-electron [LM(dithiolene)] (LM = CpMIII, Cp*MIII, (C6R6)MII) complexes are coordinatively unsaturated and usually show M-S centered cycloaddition reactions with nucleophiles (e.g. diazoalkanes, organic azides, quadricyclane) and electrophiles (e.g. tetracyanoethylene oxide, activated acetylene). The resulting metalladithiolene cycloadducts, which have three-membered M-S-C or M-S-N rings, further react with protic acids or PR3 to undergo the ring-opening reactions involving the M-C bond, M-S bond or M-N bond cleavages. Furthermore, diverse adduct dissociations are observed by thermal, photochemical or electrochemical redox reactions. Such reactions normally produce the original [LM(dithiolene)] complexes (non-adduct) and the eliminated fragments. Among them, the Co-S centered imido adduct [CpCo(dithiolene)(NR)] (R = Ts, Ms) reacted under thermal conditions in the presence of PR3 to undergo the intramolecular imido migration reaction to the Cp ligand, giving [(C5H4-NHR)Co(dithiolene)] complexes. The M-S centered multinuclear cluster complexes are obtained by the reaction of [LM(dithiolene)] with low valent M(CO)n complexes. The square-planar bis(dithiolene) complexes [M(dithiolene)2]0 (M = Ni, Pd, Pt) or tris(dithiolene) complexes [M(dithiolene)3]0 yield cycloaddition products with olefins. These reactions are due to ligand centered reactions made possible by a molecular orbital overlap between dithiolene LUMO and olefin HOMO. Similar ligand centered adducts are obtained by the reaction of dianionic [M(dithiolene)2]2− with haloalkanes or dihaloalkanes. Also these adducts of bis(dithiolene) complex are dissociated photochemically and electrochemically. This paper also describes the reactivities of organometallic o-carborane dithiolate complexes, which are generally formulated as [LM(S2C2B10H10)] (LM = CpCo, Cp*Rh, Cp*Ir, (p-cymene)Ru and (p-cymene)Os). Diverse addition reactions are reported; in particular, the reaction with acetylene involves B-H bond activation in the carborane moiety. 相似文献
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Esther von Grotthuss Felix Nawa Michael Bolte Hans-Wolfram Lerner Matthias Wagner 《Tetrahedron》2019,75(1):26-30
The 9,10-dimethyl-9,10-dihydro-9,10-diboraanthracene dianion salt Li2[1] instantaneously reacts with the dichalcogens O2(tBu)2, S2Me2, S2(pTol)2, Se2Ph2, and Te2Ph2 under reductive cleavage of the chalcogen–chalcogen bonds to give lithium chalcogenides and neutral 1. In solution, the products are involved in rapid association/dissociation equilibria. In the crystalline state, 1 and Li[O(tBu)] form a diadduct, whereas Li[SMe] gives a B?B-bridged monoadduct. In the three remaining cases, the crystal lattices contain monoadducts of 1 with one tri- and one tetracoordinate boron atom. 相似文献
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Soumen Dey 《Tetrahedron letters》2008,49(6):960-964
Two β-octabromocalix[4]pyrroles were synthesized using a modified strategy, which provides the advantage of large scale preparation with rapid purification. The acetone inclusion complexes of these compounds show different structural orientations featuring diverse types of novel hydrogen bonding owing to varied meso-substitution along with the presence of eight peripheral bromine atoms. 相似文献
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Christopher Hubrich Dirk Michalik Axel Schulz Alexander Villinger 《无机化学与普通化学杂志》2008,634(8):1403-1408
The reaction of Ph2PCl and PhPCl2 with bis(trimethylsilyl)sulfur diimide in the presence of GaCl3 and AlCl3 yields diadducts of the corresponding cyclodiphosph(V)azene: [Ph2PN]2·(GaCl3)2 ( 1 ), [Ph2PN]2·(AlCl3)2 ( 2 ), and [Ph(Cl)PN]2·(AlCl3)2 ( 3 ). This reaction is triggered by Lewis acids, which catalyse the (CH3)3Si‐Cl and S8 elimination. The structures of 1· 2 CH2Cl2, 2· 2 CH2Cl2 and 3 were determined by single crystal X‐ray studies ( 1 : triclinic, , a = 9.679(2) Å, b = 9.863(2) Å, c = 11.366(2) Å, α = 113.55(3)°; β = 99.59(3)°; γ = 106.67(3)°; V = 902.8(3) Å3, Z = 1; 2 : triclinic, , a = 9.639(2) Å, b = 9.804(2) Å, c = 11.321(2) Å, α = 113.71(3)°; β = 99.44(3)°; γ = 106.70(3)°; V = 889.3(3) Å3, Z = 1; 3 : orthorhombic, Pbca, a = 14.853(3) Å, b = 9.261(2) Å, c = 16.631(3) Å, V = 2287.7(8) Å3, Z = 4. 相似文献
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Ju-Hyung Chae Minyeong Choi Semin Son Su-Min Ko Prof. In-Hwan Lee 《Angewandte Chemie (International ed. in English)》2023,62(31):e202305414
Precise control of multiple structural parameters associated with vinyl polymers is important for producing materials with the desired properties and functions. While the development of living polymerization methods has provided a way to control the various structural parameters of vinyl polymers, the concomitant control of their sequence and regioregularity remains a challenging task. To overcome this challenge, herein, we report the living cationic ring-opening polymerization of hetero Diels–Alder adducts. The scalable and modular synthesis of the cyclic monomers was achieved by a one-step protocol using readily available vinyl precursors. Subsequently, living polymerization of the cyclic monomers was examined, allowing the synthesis of vinyl polymers while controlling multiple factors, including molecular weight, dispersity, alternating sequence, head-to-head regioregularity, and end-group functionality. The living characteristics of the developed method were further demonstrated by block copolymerization. The synthesized vinyl polymers exhibited unique thermal properties and underwent fast photodegradation even under sunlight. 相似文献
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Florian Breitsameter Hans-Peter Schrdel Alfred Schmidpeter Heinrich Nth Susana Rojas-Lima 《无机化学与普通化学杂志》1999,625(8):1293-1300
Ylide Adducts of Pentele Trichlorides Ylides Ph3PCR2 form 1 : 1 adducts with PCl3, AsCl3 und SbCl3. The addition of HCl to dichlorophosphanyl- und dichloroarsanyl ylides also leads to such adducts. In solution the PCl3 adducts 2 are dissociated into ions. For the AsCl3 adducts 3 b and 3 e of triphenylphosphonium ethylide and isopropylide X-ray analyses show distinctly different degrees of transition from a zwitterionic ψ-tbp to a cationic ψ-tetrahedral structure. The SbCl3 adduct 4 b of the triphenylphosphonium ethylide on the other hand forms a rather asymmetric dimer and approaches a square-pyramidal geometry at the antimony atom. The 2 : 1 ylide adducts 11 with PCl3 form in solution the dications (Ph3PCR2)2PCl2+. The 2 : 3 adduct 15 of triphenylphosphonium methylide to AsCl3 also has an ionic structure in the crystal. There are cations (Ph3PCH2)2AsCl2+, which pairwise join with two AsCl3 molecules to form doubly charged supracations in the presence of As2Cl82– as counterions. 相似文献
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The formal GaCl3-assisted [3+2] cycloaddition of two (Me3Si)2N–N(SiMe3)–PCl2 molecules resulting in the formation of a triazadiphosphole has been studied by means of B3LYP/6-31G(d,p) computations. These calculations revealed a stepwise reaction mechanism starting from the disguised 1,3-dipole and dipolarophile
(Me3Si)2N–N(SiMe3)–PCl2. Comparison of the potential energy surface for the formation of a triazadiphosphole in the presence and without a Lewis
acid indicate, that addition of a Lewis acid such as GaCl3 decreases the activation barriers to Me3Si–Cl elimination, in accord with experiment.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献