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Book ChapterDOI

Transition Metal Complexes Containing Bidentate Phosphine Ligands

01 Jan 1972-Advances in Inorganic Chemistry and Radiochemistry (Academic Press)-Vol. 14, pp 173-253
TL;DR: In this paper, several transition metal complexes containing bidentate phosphine ligands are described, and a major complication in diphosphine complexes is the relative complexity of the ligands.
Abstract: Publisher Summary This chapter describes several transition metal complexes containing bidentate phosphine ligands. The bonding in metal–phosphine ligands due to the formation of π-type bonds between the metal and phosphorus atoms. Several techniques are used to study metal–phosphine complexes. These techniques include mass spectroscopy infrared spectroscopy, nuclear magnetic resonance, electronic spectroscopy, electron spin resonance, and Mossbauer spectroscopy. A major complication in diphosphine complexes is the relative complexity of the ligands. When a diphosphine complexes with a metal ion, the electron density on the phosphorus atom changes, and the ligand is restricted in the conformation it can assume. Thus the vibrational spectra of the free and coordinated ligands differ.
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Journal ArticleDOI
TL;DR: The transition metal coordination and organometallic chemistry of acyclic diphosphazane ligands has grown rapidly in the last two decades and a stage has been reached that permits a delineation of similarities and contrasts with the chemistry of Diphosphinomethane type ligands.

221 citations

Journal ArticleDOI
TL;DR: In this article, a 1:2-Komplexe with AuCl, Aul, and AuCH3 is described, and the results are of interest with respect to the short but nonbonding AuAu distance.
Abstract: Bis(diphenylphosphino)methan bildet 1:2-Komplexe mit AuCl, Aul und AuCH3 (1a–c). Auch von 2,2-Bis(diphenylphosphino)propan kann ein analoger AuCl-Komplex erhalten werden (2a). Zusatzlich zur ublichen analytischen und spektroskopischen Charakterisierung werden Au-Mosbauer- und Au-ESCA-Spektren aufgenommen und von 1a eine Rontgenstrukturanalyse angefertigt. Die Ergebnisse sind wegen des kurzen, aber nichtbindenden AuAu-Abstandes von Interesse. Gold Complexes of Diphosphinomethanes, I. Synthesis and Crystal Structure of Binuclear Gold(I) Compounds Bis(diphenylphosphino)methane forms 1:2 complexes of AuCl, Aul, and AuCH3 (1a–c). From 2,2-bis(diphenylphosphino)propane an analogous AuCl complex could also be obtained (2a). in addition to the usual analytical and spectroscopic characterization, Au-Mosbauer and Au-ESCA spectra have been recorded, and an X-ray analysis of 1a has been carried out. The results are of interest with respect to the short, but nonbonding AuAu distance.

171 citations

Journal ArticleDOI
TL;DR: The 1:1-komplex of AgBr with bis(diphenylphosphino)methane (dppm) was first reported in this article, where the structure consists of discrete bromide anions and trinuclear cations.
Abstract: Der 1:1-Komplex aus AgBr und Bis(diphenylphosphino)methan (dppm) kristallisiert in der orthorhombischen Raumgruppe Pna21 mit a = 1910(1), b = 2147(1) und c = 1858(1) pm (Z = 4). Seine Struktur besteht aus diskreten Bromid-Anionen und dreikernigen Kationen [Ag3Br2(dppm)3]+, deren Grundelement eine trigonale Bipyramide mit den Ag-Atomen in den aquatorialen und den Br-Atomen in den axialen Positionen ist. Jeder dppm-Ligand verbruckt eine Seite des Ag3-Dreiecks. Der 2:1-Komplex aus AgBr und Bis(diphenylphosphino)-methylamin (dppa) kristallisiert in der monoklinen Raumgruppe P21/c mit a = 1136,0(7), b = 1603,3(12), c = 1689,1 (12) pm und β = 122,36(4)° (Z = 4). Das Grundelement seiner Struktur ist eine tetragonale Bipyramide mit vier Ag-Atomen in den aquatorialen und zwei Bromid-Atomen in den axialen Positionen. Die AgAg-Kanten werden abwechselnd durch Br-Atome und dppa-Liganden uberbruckt. Allgemeine geometrische Beziehungen von Strukturparametern in Komplexen mit Diphosphinomethan und ahnlichen Liganden werden abgeleitet und diskutiert. Contributions to the Structural Chemistry of Silver Halide-Diphosphinomethane and Related Complexes The 1:1-complex of AgBr with bis(diphenylphosphino)methane (dppm) crystallizes in the orthorhombic space group Pna21 with a = 1910(1), b = 2147(1) and c = 1858(1) (Z = 4). Its structure consists of discrete bromide anions and trinuclear cations [Ag3Br2(dppm)3]+. The basic unit is a trigonal bipyramid with the Ag atoms in the equatorial and the Br atoms in the axial positions. Each dppm ligand bridges an edge of the Ag3 triangle. The 2:1-complex of AgBr with bis (diphenylphosphino)methylamine (dppa) crystallizes in the monoclinic space group P21/c with a = 1136.0(7), b = 1603.3(12), c = 1689.1(12) pm and β = 122.36(4)° (Z = 4). The basic unit of its structure is a tetragonal bipyramid with four Ag atoms in the equatorial and the bromine atoms in the axial positions. The AgAg edges are alternatingly bridged by bromine atoms and dppa ligands. Some general relations between structural parameters in complexes with diphosphinomethane and related ligands are deducted and discussed.

49 citations

References
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TL;DR: The 1,1′-dilithioferrocene can be used in situ, or when isolated as the pyrophoric adduct [(C 5 H 4 Li) 2 Fe]·TMEDA, to prepare the following complexes in high yields: ferrocene-1, 1, 1′-bis(dimethylarsine) (Fdma), ferrocenophane, Fdpa, Fdt, Fydioxene, and Fdmp, which can be converted quantitatively to Fdt by reduction with lithium aluminum hydr

369 citations

Journal ArticleDOI
TL;DR: In this paper, the s-component of the platinum-phosphorus bonds is analyzed in terms of the trans-effect of the ligand to weaken the bond trans to itself and its relation to the trans effect is considered.
Abstract: The 195Pt–31P nuclear spin coupling constants, ranging between 1462 and 5698 c./sec., of twenty-five platinum complexes are reported and discussed in terms of the s-component of the platinum–phosphorus bonds. The trans-influence is defined as the tendency of a ligand to weaken the bond trans to itself, and its relation to the trans-effect is considered. It is shown that the high trans-influence of phosphorus is probably due to a σ-bonding mechanism and makes a significant contribution to the high trans-effect of phosphorus ligands. Some 31P chemical shifts are reported.

187 citations

Journal ArticleDOI
TL;DR: In this paper, wechselwirkung der Diphosphine mit elementarem Jod bzw. Brom fuhrt zu Jodphosphinen, R2PJ, Bzw., R4P2R′]J, an, wahrend im Tetracycloalkyl-diphosphin die PP-Brucke gespalten wird.
Abstract: Aliphatische und cycloaliphatische Chlorphosphine, R2PCl, fur die ein allgemein anwendbares Darstellungsverfahren beschrieben wird, reagieren mit Natrium in Dioxan unter Bildung von Diphosphinen, R2PPR2. Auf diese Weise werden aus (C2H5)2PCl, (C4H9)2PCl und (C6H11)2PCl die Verbindungen (C2H5)2PP(C2H5)2, (C4H9)2PP(C4H9)2 und (C6H11)2PP(C6H11)2 dargestellt, die sich mit Schwefel bzw. Sauerstoff zu den entsprechenden Disulfiden, R2P(S)P(S)R2, bzw. Dioxyden, R2P(O)P(O)R2, vereinigen. Die Tetraalkyldiphosphine lagern ein Mol. Alkylhalogenid unter Bildung von Pentaalkyldiphosphoniumhalogeniden, [R4P2R′]J, an, wahrend im Tetracycloalkyl-diphosphin die PP-Brucke gespalten wird. — Die Wechselwirkung der Diphosphine mit elementarem Jod bzw. Brom fuhrt zu Jodphosphinen, R2PJ, bzw. Bromphosphinen, R2PBr.

159 citations