0000000000384437
AUTHOR
Tapani A. Pakkanen
Synthesis, electrochemical and theoretical studies of the Au(i)-Cu(i) heterometallic clusters bearing ferrocenyl groups
Treatment of the polymeric alkynyl compounds (AuC2R)n (R = Fc, C6H4Fc; Fc = ferrocenyl) with the diphosphine PPh2C6H4PPh2 gave complexes (RC2Au)PPh2C6H4PPh2(AuC2R) (1, R = Fc; 2, R = C6H4Fc) with end-capped ferrocenyl groups. The reactions of 1 or 2 with Cu(NCMe)4PF6 result in formation of the heterotrimetallic aggregates [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (3, R = Fc; 4, R = C6H4Fc), which consist of the alkynyl clusters [Au3Cu2(C2R)6]−“wrapped” by the cationic [Au3(PPh2C6H4PPh2)3]3+“belt”. The novel compounds were characterized by NMR spectroscopy and ESI-MS measurements. The solid state structure of 3 is reported. Electrochemical properties of the complexes 1–4 have been studied. Th…
Ferrocenyl-functionalized tetranuclear gold(I) and gold(I)-copper(I) complexes based on tridentate phosphanes
Tetranuclear AuI–FeII dimetallic and AuI–CuI–FeII trimetallic complexes bearing ferrocenyl (Fc) groups have been assembled by using two triphosphane ligands, namely, (PPh2CH2)2PPh (dpmp) and (PPh2)3CH (tppm). The compositions and structural type of the clusters are dependent on the stereochemistry of the P donor ligands. The complexes [tppmAu3Cu(C2R)3]PF6 [R = Fc (1) and 4-C6H4-Fc (2)] adopt a trigonal pyramidal {Au3Cu} arrangement of the coordinating metal core, whereas for the compounds with the linear triphosphane [Au4(dpmp)2(C2R)2](PF6)2 [R = Fc (3) and 4-C6H4-Fc (4)], a planar rhomboidal {Au4} framework was found. Clusters 1–4 were characterized by NMR spectroscopy and ESI-MS measureme…
Sky-Blue Luminescent Au(I)-Ag(I) Alkynyl-Phosphine Clusters
Treatment of the (AuC2R)n acetylides with phosphine ligand 1,4-bis(diphenylphosphino)butane (PbuP) and Ag(+) ions results in self-assembly of the heterobimetallic clusters of three structural types depending on the nature of the alkynyl group. The hexadecanuclear complex [Au12Ag4(C2R)12(PbuP)6](4+) (1) is formed for R = Ph, and the octanuclear species [Au6Ag2(C2R)6(PbuP)3](2+) adopting two structural arrangements in the solid state were found for the aliphatic alkynes (R = Bu(t) (2), 2-propanolyl (3), 1-cyclohexanolyl (4), diphenylmethanolyl (5), 2-borneolyl (6)). The structures of the compounds 1-4 and 6 were determined by single crystal X-ray diffraction analysis. The NMR spectroscopic st…
Toward luminescence vapochromism of tetranuclear AuI-Cu I clusters
A family of triphosphine gold–copper clusters bearing aliphatic and hydroxyaliphatic alkynyl ligands of general formula [HC(PPh2)3Au3Cu(C2R)3]+ (R = cyclohexyl (1), cyclopentyl (2), But (3), cyclohexanolyl (4), cyclopentanolyl (5), 2,6-dimethylheptanolyl (6), 2-methylbutanolyl (7), diphenylmethanolyl (8)) was synthesized via a self-assembly protocol, which involves treatment of the (AuC2R)n acetylides with the (PPh2)3CH ligand in the presence of Cu+ ions and NEt3. Addition of Cl– or Br– anions to complex 8 results in coordination of the halides to the copper atoms to give neutral HC(PPh2)3Au3CuHal(C2COHPh2)3 derivatives (Hal = Cl (9), Br (10)). The title compounds were characterized by NMR …
Solid-state luminescence of Au-Cu-alkynyl complexes induced by metallophilicity-driven aggregation.
A new series of homoleptic alkynyl complexes, [{Au2Cu2(C2R)4}n] (R=C3H7O (1), C6H11O (2), C9H19O (3), C13H11O (4)), were obtained from Au(SC4H8)Cl, Cu(NCMe)4PF6, and the corresponding alkyne in the presence of a base (NEt3). Complexes 1-4 aggregate upon crystallization into polymeric chains through extensive metallophilic interactions. The cluster that contains fluorenolyl functionalities, C13H9O (5), crystallizes in its molecular form as a disolvate, [Au2Cu2(C2C13H9O)4]·2THF. The substitution of weakly bound THF molecules with pyridine molecules leads to the complex [Au2Cu2(C2C13H9O)4]·2py (6), thus giving two polymorphs in the solid state. Such structural diversity is established through …
Electrochemically assisted anion insertion in Au(I)–Cu(I) heterotrimetallic clusters bearing ferrocenyl groups: Application to the fluoride/chloride discrimination in aqueous media
The heterotrimetallic Au(I)–Cu(I) aggregate [{Au3Cu2(C2C6H4Fc)6}Au3(PPh2C6H4PPh2)3](PF6)2 exhibits a well-defined solid state electrochemistry in contact with aqueous media, based on ferrocenyl-centred oxidation processes involving anion insertion. Upon attachment of microparticulate deposits of the cluster to graphite electrodes, distinctive electrochemical responses can be obtained for fluoride and chloride ions in aqueous media. Keywords: Heterometallic clusters, Gold, Copper, Fluoride/chloride discrimination, Electrochemical anion insertion
Triphosphine-supported bimetallic Au(I)-M(I) (M = Ag, Cu) alkynyl clusters.
The reactions of gold acetylides (AuC2R)n with triphosphine ligands PPh2-(CH2)n-PPh-(CH2)2-PPh2 (n = 1, dpmp; 2, dpep) in the presence of M(+) ions (M = Cu, Ag) lead to an assembly of the heterometallic clusters, the composition of which is determined by the steric bulkiness of the alkynyl groups and the flexibility of the phosphine motifs. For R = Ph, an unprecedented hexanuclear complex [Au5Cu(C2R)4(dpmp)2](2+) (1) was isolated, while for the aliphatic alkynes (R = 1-cyclohexanolyl, 2-borneolyl, 2,6-dimethyl-4-heptanolyl) a family of compounds based on a tetrametallic framework was prepared, [Au3Cu(C2R)3(dpmp)](+) (2, R = 1-cyclohexanolyl), [Au3M(C2R)3(dpep)]2(+2) (3, M = Cu, R = 1-cycloh…
Determination of Individual Gibbs Energies of Anion Transfer and Excess Gibbs Energies Using an Electrochemical Method Based on Insertion Electrochemistry of Solid Compounds
A method is presented to determine, individually and with minimal extra-thermodynamic assumptions, the Gibbs energy for anion transfer between two solvents using solid state electrochemistry of alkynyldiphosphine dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1, R = Fc; L2, R = C6H4Fc) and the heterometallic Au(I)–Cu(I) [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3, R = Fc; L4, R = C6H4Fc) cluster complexes containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes, based on ferrocenyl-centered oxidation processes involving anion insertion. Voltammetric data can be used for a direct measurement of…
Experimental and computational investigation on the formation pathway of [RuCl2(CO)2(ERR′)2] (E = S, Se, Te; R, R′ = Me, Ph) from [RuCl2(CO)3]2 and ERR′
The pathways to the formation of the series of [RuCl2(CO)2(ERR′)2] (E = S, Se, Te; R, R′ = Me, Ph) complexes from [RuCl2(CO)3]2 and ERR′ have been explored experimentally in THF and CH2Cl2, and computationally by PBE0-D3/def2-TZVP calculations. The end-products and some reaction intermediates have been isolated and identified by NMR spectroscopy, and their crystal structures have been determined by X-ray diffraction. The relative stabilities of the [RuCl2(CO)2(ERR′)2] isomers follow the order cct > ccc > tcc > ttt ≈ ctc (the terms c/t refer to cis/trans arrangement of the ligands in the order of Cl, CO, and ERR′). The yields were rather similar in both solvents, but the reactions were signi…
Estimation of free energies of anion transfer from solid-state electrochemistry of alkynyl-based Au(I) dinuclear and Au(I)–Cu(I) cluster complexes containing ferrocenyl groups
A method is presented to determine the free energy for anion transfer between two solvents. This is based on solid-state electrochemistry of alkynyl-based dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1: R=Fc; L2: R=C6H4Fc) and heterometallic Au(I)–Cu(I) [{Au3Cu2 (C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3: R=Fc; L4: R=C6H4Fc) complexes. These compounds exhibit a reversible ferrocenyl-centred solid-state oxidation processes involving anion insertion in contact with aqueous, MeOH and MeCN electrolytes. Voltammetric data can be used for a direct measurement of the free energy of ion transfer using midpeak potentials in solutions of suitable salts in the solvents separately or in mixtures of the s…
CCDC 955945: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v
CCDC 962935: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 962936: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 883708: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v
CCDC 904087: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v
CCDC 962938: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 937899: Experimental Crystal Structure Determination
Related Article: Thuy Minh Dau, Julia R. Shakirova, Antonio Doménech, Janne Jänis, Matti Haukka, Elena V. Grachova, Tapani A. Pakkanen, Sergey P. Tunik, Igor O. Koshevoy|2013|Eur.J.Inorg.Chem.||4976|doi:10.1002/ejic.201300615
CCDC 937897: Experimental Crystal Structure Determination
Related Article: Thuy Minh Dau, Julia R. Shakirova, Antonio Doménech, Janne Jänis, Matti Haukka, Elena V. Grachova, Tapani A. Pakkanen, Sergey P. Tunik, Igor O. Koshevoy|2013|Eur.J.Inorg.Chem.||4976|doi:10.1002/ejic.201300615
CCDC 938077: Experimental Crystal Structure Determination
Related Article: Igor O. Koshevoy, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, and Tapani A. Pakkanen|2013|Inorg.Chem.|52|3663|doi:10.1021/ic302105a
CCDC 938080: Experimental Crystal Structure Determination
Related Article: Igor O. Koshevoy, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, and Tapani A. Pakkanen|2013|Inorg.Chem.|52|3663|doi:10.1021/ic302105a
CCDC 938078: Experimental Crystal Structure Determination
Related Article: Igor O. Koshevoy, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, and Tapani A. Pakkanen|2013|Inorg.Chem.|52|3663|doi:10.1021/ic302105a
CCDC 962933: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 872767: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v
CCDC 962934: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 962937: Experimental Crystal Structure Determination
Related Article: Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Chou, Igor O. Koshevoy|2014|Dalton Trans.|43|3383|doi:10.1039/C3DT52658E
CCDC 938079: Experimental Crystal Structure Determination
Related Article: Igor O. Koshevoy, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, and Tapani A. Pakkanen|2013|Inorg.Chem.|52|3663|doi:10.1021/ic302105a
CCDC 937898: Experimental Crystal Structure Determination
Related Article: Thuy Minh Dau, Julia R. Shakirova, Antonio Doménech, Janne Jänis, Matti Haukka, Elena V. Grachova, Tapani A. Pakkanen, Sergey P. Tunik, Igor O. Koshevoy|2013|Eur.J.Inorg.Chem.||4976|doi:10.1002/ejic.201300615
CCDC 872766: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v
CCDC 938076: Experimental Crystal Structure Determination
Related Article: Igor O. Koshevoy, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, and Tapani A. Pakkanen|2013|Inorg.Chem.|52|3663|doi:10.1021/ic302105a
CCDC 955946: Experimental Crystal Structure Determination
Related Article: Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy|2013|Organometallics|32|4061|doi:10.1021/om301100v