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.

Gold-Komplexe von Diphosphinomethanen, I. Synthese und Kristallstruktur zweikerniger Gold(I)-Verbindungen

A brief account of the methods generally employed for the synthesis of metal alkoxides has been presented. Successful elucidation of the structural features of simple alkoxides on the basis of a coordination model involving alkoxy bridges has prompted a detailed study of a variety of bimetallic alkoxides during the last two decades followed by the extension of the work to a novel series of ter- and tetra-metallic alkoxides during the last two years. Most of these polymetallic alkoxides (including derivatives of strongly electropositive alkali, alkaline earth metals and lanthanons) are stable to heat and can be volatilized unchanged. After listing the typical properties and reactions of these alkoxy derivatives, their hydrolytic reactions are briefly discussed. The uses of metallic alkoxides for ceramic materials and the potential applications of bimetallic alkoxides in this direction are discussed.

Synthesis and reactions of metal alkoxides

Organometallic conformational equilbria : XVI. Steric effects on π-allyl and π-indenyl orientation in molybdenum and tungsten complexes

Publisher Summary This chapter focuses on the insertion of carbon monoxide (CO) into transition metal–carbon σ bonds. An attempt is made at a complete literature coverage of the insertion of CO. Numerous organometallic reactions conform to the general equation M–X + Y → M–Y–X, where M is a metal and X and Y are monatomic or polyatomic species. Such processes are termed as “insertion reactions.” The chapter also compares relative reactivities and the activation parameters for the CO insertion of various types of metal alkyls. The elimination of carbon monoxide accompanied by the conversion of an acyl group to the corresponding alkyl moiety has been termed as “decarbonylation.” This is the most extensively, as well as intensively, studied type of decarbonylation. The ultraviolet light-induced decarbonylation has been successfully effected in several types of transition metal acyls. In some instances, the decarbonylation can be effected, under mild conditions, using a stoichiometric amount of a CO-abstracting metal complex. The intramolecular nature of carbon monoxide insertion is demonstrated by the ability of ligands (L) other than CO to convert an alkyl metal carbonyl to the corresponding acyl complex.

Insertion Reactions of Transition Metal-Carbon σ-Bonded Compounds I: Carbon Monoxide Insertion

R.B. King

Papers

Preparation and characterization of some volatile double isopropoxides of aluminum with alkaline earth metals

Complexes of trivalent phosphorus derivatives. XIV. Metal complexes of diphenylphosphinophenylacetylene

Reactions of alkali-metal derivatives of metal carbonyls. IX. Preparation and properties of allyl derivatives of cyclopentadienylruthenium carbonyl

Complexes of trivalent phosphorus derivates. IV. Metal carbonyl complexes of cis-bis-1,2,-(diphenylphosphino) ethylene.☆

Complexes of trivalent phosphorus derivatives. XIII. 1,4-bis(diphenylphosphino)butyne-2 and its complexes