Ilpo Tahvanainen

Bio: Ilpo Tahvanainen is an academic researcher from University of Eastern Finland. The author has contributed to research in topics: Inorganic compound & Absorption spectroscopy. The author has an hindex of 3, co-authored 4 publications receiving 49 citations.

Mixed-metal cluster derivatives of Co3(μ3-CPh)(CO)9: Crystal structures of Co3(μ3-CPh)(CO)9, HFeCo2(μ3-CPh)(CO)9, and FeCo2(μ-AuPPh3)(μ3-CPh)(CO)9

Abstract: The compound Co 3 (μ 2 -CPh)(CO) 9 ( 1 ) reacts with Na 2 [Fe(CO) 4 ] in tetrahydrofuran to afford the mixed-metal hydride cluster HFeCo 2 (μ 3 -CPh)(CO) 9 ( 2 ) after acid treatment. The structures of 1 and 2 have been determined by X-ray diffraction. The cluster 1 crystallizes in space group P 1 ( Z = 4) with a 8.034(3), b 15.760(7), c 15.900(7) A, α 101.11(3), β 100.99(3), γ 100.13(3)°, and the cluster 2 in the space group C 2/ c ( Z = 8) with a 14.114(4), b 7.804(3), c 33.844(12) A, β 96.13(3)°. The two structures are similar, with a M 3 triangle triply bridged by the alkylidyne carbon atom and with three terminal carbonyl ligands bonded to each metal atom. The hydride ligand in 2 could not be located from the difference Fourier maps, but the structure of its gold triphenylphosphine derivative FeCo 2 (μ-AuPPh 3 )(μ 3 -CPh)(CO) 9 ( 3 ), which was synthesized in toluene by a direct reaction of 2 with Au(PPh 3 )Cl in the presence of TlPF 6 , indicates that the hydride ligand is in an edge bridging position. The cluster 3 crystallizes in space group Pna 2 1 ( Z = 4) with a 34.617(6), b 8.793(2), c 11.226(2) A.

Coordination complexes of silver(I) with tertiary phosphine and related ligands

Abstract: This paper gives an overview of the structural chemistry of silver(I) coordination complexes. The main discussion is on the halide complexes (F−, Cl−, Br−, I−) but included are also the pseudo-halides (CN−, SCN−) and the classical non-coordinating anions (NO3−, ClO4−, BF4−, PF6−) and oxy-anions (NO3−, H3CCO2−, F3CCO2−, F3CSO3−, etc.). The main focus is on complexes of these silver(I) salts with phosphine ligands, but where relevant the chemistry of other donor ligands is also reviewed. Coordination complexes of silver(I) halides show a rich variation of structural types. The type of structure depends on the stoichiometry of the ligand to silver in the reaction mixture, as well as reaction conditions. Other factors influencing the structure of these complexes include the halide or pseudo-halide ligands used as counterion and the type of solvent.

Heteronuclear Cluster Chemistry of Copper, Silver, and Gold

Abstract: Publisher Summary This chapter reviews the synthesis, structures, chemical properties, and dynamic behavior of copper, silver, and gold—containing heteronuclear cluster compounds. A cluster compound is considered to be a species, which contains three or more framework atoms with sufficient interactions among them to define either a metal core made up of one or more trigonal planar M 3 units or a three-dimensional skeletal geometry based on a wide variety of polyhedra. The chapter is restricted Group IB metal cluster compounds in which the skeletal atoms consist predominantly of transition metals. In the vast majority of the Group IB metal heteronuclear clusters reported so far, one two-electron donor ligand is attached to each coinage metal and PR 3 is the most common ligand of this type. A number of species with coinage metals that do not carry any ligands or with ligands that are not simple two-electron donors bonded to the Group IB metals are also known and these clusters are also described in this chapter.

Heteronuclear Gold Cluster Compounds

Abstract: Publisher Summary The development of the area of heteronuclear gold cluster chemistry can be traced to the pioneering work of Lewis and Nyholm, who reported the first syntheses and crystallographic determinations of compounds, containing gold–metal bonds in a series of articles from 1964 onward. The chapter presents a table presenting the examples of the compounds that have been structurally characterized by X-ray methods and are considered to exhibit gold–heterometal bonding interaction. This chapter explains the current literature relevant to heteronuclear cluster compounds, containing gold–metal bonds, with particular emphasis being placed on those clusters that contain a high proportion of gold in the metal framework. The most widely exploited synthetic route used in the formation of gold–metal bonds involves addition of the gold center as the gold phosphine fragment AuPR3. The first examples of homonuclear gold cluster compounds were obtained by the reduction of gold(I) phosphine complexes, using solutions of borohydride. The addition of gold phosphine fragments to transition metal compounds is readily extended to include reactions of heteronuclear gold cluster compounds and has been used to build up clusters of increasing nuclearity. Heteronuclear gold cluster compounds have been proposed as potential precursors for the synthesis of selective catalysts and also as models of the modifications to the substrate that arise at a the molecular level.

Coordination chemistry of the solvated AgI and AuI ions in liquid and aqueous ammonia, trialkyl and triphenyl phosphite, and tri-n-butylphosphine solutions.

Abstract: The coordination chemistry of solvated Ag(I) and Au(I) ions has been studied in some of the most strong electron-pair donor solvents, liquid and aqueous ammonia, and the P donor solvents triethyl, tri-n-butyl, and triphenyl phosphite and tri-n-butylphosphine. The solvated Ag(I) ions have been characterized in solution by means of extended X-ray absorption fine structure (EXAFS), Raman, and (107)Ag NMR spectroscopy and the solid solvates by means of thermogravimetry and EXAFS and Raman spectroscopy. The Ag(I) ion is two- and three-coordinated in aqueous and liquid ammonia solutions with mean Ag-N bond distances of 2.15(1) and 2.26(1) A, respectively. The crystal structure of [Ag(NH3)3]ClO4.0.47 NH3 (1) reveals a regular trigonal-coplanar coordination around the Ag(I) ion with Ag-N bond distances of 2.263(6) A and a Ag...Ag distance of 3.278(2) A separating the complexes. The decomposition products of 1 have been analyzed, and one of them, [Ag(NH3)2]ClO4, has been structurally characterized by means of EXAFS, showing [Ag(NH3)2] units connected into chains by double O bridges from perchlorate ions; the Ag...Ag distance is 3.01(1) A. The linear bisamminegold(I) complex, [Au(NH3)2]+, is predominant in both liquid and aqueous ammonia solutions, as well as in solid [Au(NH3)2]BF4, with Au-N bond distances of 2.022(5), 2.025(5), and 2.026(7) A, respectively. The solvated Ag(I) ions are three-coordinated, most probably in triangular fashion, in the P donor solvents with mean Ag-P bond distances of 2.48-2.53 A. The Au(I) ions are three-coordinated in triethyl phosphite and tri-n-butylphosphine solutions with mean Au-P bond distances of 2.37(1) and 2.40(1) A, respectively.