COORDINATION COMPOUNDS OF THE TRANSITION METALS AS RELATED TO THE CATALYTIC PROCESS AND TO THE SYNTHESIS OF NEW MATERIALS.

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)