Numerous new metal halide, carbonyl, and cyclopentadienyl complexes of the chelating tritertiary phosphine bis(2-diphenylphosphinoethyl) phenylphosphine and the chelating tetratertiary phosphines 1,1,4,7,10, 10-hexaphenyl-1,4,7,10-tetraphosphadecane and tris(2-diphenylphosphinoethyl) phosphine are described. Some preliminary studies of reactions of metal carbonyl derivatives with diphenylvinylphosphine are discussed. Metal complexes of the acetylenic tertiary phosphines (C6H5)2PCH2CCCH2P(C6H5)2 and (C6H5)2PCCC6H5 are described. A few reactions of tris(dimethylamino)arsine with various metal carbonyls are summarized; these resulted in the preparation of the first derivative with two tris(dimethylamino)arsine ligands attached to a single metal atom. The mixed phosphine-isonitrile and arsine-isontrile ligands (C6H5)2ECH2CH2NC(E = P or As) have been prepared by the base-catalyzed addition of (C6H5)2EH(E = P or As) to vinyl isocyanide; these are the first known compounds containing both tertiary phosphine (or arsine) and isonitrile groups. Some new compounds have been obtained from pentacarbonyliron and the diacetylenes 1,7-cyclotridecadiyne, 1,8-cyclotetradecadiyne, and 2,4-hexadiyne. Possible aerospace applications of this research are discussed. (Author).

Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.

The base-catalyzed addition of phosphorus-hydrogen and arsenic-hydrogen bonds to the carbon-carbon multiple bonds in vinylphosphines and ethynylphosphines provides a useful new method for the synthesis of novel polytertiary phosphines and phosphine-arsines. Using this method the authors have prepared in large quantities and studied the coordination chemistry of the tritertiary phosphine ((C6H5)2PCH2CH2)2PC6H5, the two isomeric tetratertiary phosphines (C6H5)2PCH2CH2P(C6H5)CH2CH2P(C6H5)CH2CH2P(C6H5)2 and ((C6H5)2PCH2CH2)3P, and the hexatertiary phosphine ((C6H5)2PCH2CH2)2PCH2CH2P(CH2CH2P(C6H5)2)2. This preparative method also provides convenient syntheses of the mixed phosphine-arsines as (C6H5)2PCH2CH2As(C6H5)2. A similar base-catalyzed addition of (C6H5)2EH (E = P or As) to vinyl isocyanide gives the novel isocyanide derivatives (C6H5)2ECH2CH2NC (E = P or As). However, base-catalyzed addition of C6H5PH2 to vinyl isocyanide results in 1,4-addition to give the new phosphorus-carbon-nitrogen heterocycle 1-phenyl-4,5-dihydro-3-azaphosphole. This report also describes transition metal complexes of the ligands (C6H5)2PCCC6H5, (C6H5)2PCH2CCCH2P(C6H5)2, ((CH3)2N)3E (E = P or As), and (p-(CH3)2NC6H4)nP(C6H5)(3-n) (n =1, 2, and 3). (Author).

The development of a new class of phosphine-alkene and thio-phosphine-alkene ligands based on a chalcone ferrocene framework, represents the primary focus of this study. The synthesis and characterisation of novel ligands, ferrochalcone 32 and thio-ferrochalcone 33, are described. The related alkene-phosphine ligands, the Lei ligand 17 and novel thio-Lei ligand 46, are further detailed. The coordination chemistry of four ligands (17, 32, 33 and 46) with various transition metals (Pt, Pd, Cu, Rh and Au) has been investigated in a comprehensive spectroscopis study. Single crystal X-ray analysis has been conducted at suitable junctures within the project. A surprising finding was that some solution-state structures were found to be different when studied in the solid state. The AuI complexes-containing the ligands have been successfully used in 1,5-enyne cycloisomerisation reactions. In addition to the coordination chemistry of the novel ligand systems, some interesting findings emerged For example, AuI complex of Lei ligand 17 and monodbaPHOS 74 undergoes an interesting solid-state [2+2] intramolecular cycloaddition transformation, giving cycloadduct, 72 and 77. An interesting finding includes the presence of impurity in commercially available Pd(OAc)2. Cyclopalladation of papaverine was carried out using pure and impure Pd(OAc)2, which resulted in the identification of novel Pd-dimer complex, 86. The result suggest that nitrite contaminants derive from impurities in Pd(OAc)2, and not from the oxidation of acetonitrile mediated by metallic Pd0, explain the formation of PdII-nitrito cyclopalladated products. Photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex 90 was also observed.