Transition metal chemistry of phosphorus based ligands: Bis(diaryloxyphosphino)amine ligands and their palladium(II) and platinum(II) derivatives

976-978The reactions of bis(phosphines) of the type X2PN(Ph)PX2 (1 X2=O2C2H4, 2 X=OCH2C6H5, 3 X2=O2C6H4) with [M(COD)Cl2] (M=Pd or Pt) in dichloromethane afford both mono- and binuclear complexes in good yield. All the compounds are characterized by NMR (1H and 31P) and IR spectroscopic data and by elemental analysis

Derivatisation and transition metal chemistry of a new monophosphinite ligand: 2-(diphenylphosphinoxy)naphthyl

1390-1394Reaction of monophosphinite ligand, 2-(diphenylphosphinoxy) naphthyl, C10H7PPh2 (1) with elemental sulphur or selenium gives the corresponding sulphide C10H7OP(S)Ph2 (2) or selenide C10H7OP(Se)ph2 (3) derivatives. Reaction of 1 with [CpRu(PPh3)2Cl] gives monosubstituted complex, [CpRu(C10H7OPPh2)(PPh3)C1] (4) as well as the disubstituted complex. [CpRu(C10H7PPh2)2Cl] (5) depending upon the reaction conditions. Treatment of 1 with [Rh(CO)2Cl]2 affords a trans-complex, [Rh(CO)(C10H7PPh2Cl] (6). Reaction of 1 with [Pd(COD)Cl2] results in the formation of an unexpected chlorobridged dipalladium complex: [Pd (PPh2O)( PPh2OH)(μ-Cl)]2 (7), whereas similar reaction with [pt(COD)Cl2] gives cis-[Pt(C10H7PPh2)2Cl2] (8) in good yield

Synthesis of phenylan1ino bis(dichlorophosphine oxide) and its complexes with group 12 metals

539-541The high yield one pot synthesis of bis (dichlorophosphinoyl) aniline, PhN[P(O)Cl2]2 and its complexes with group 12 metals is described. &nbsp

Organometallic derivatives of diphosphazanes. 2. Seven-coordinated Group 6 metal tricarbonyl complexes of diphosphazane ligands. X-ray crystal structure of [WI2(CO)3{P(OPh)2}2NPh]

The reactions of the complexes [MI2(CO)3-(NCMe)2] (M = Mo, W) with the diphosphazane ligands RN{P(OPh)2}2 (R = Me, Ph) in CH2Cl2 at room temperature afford new seven-coordinated complexes of the type [MI2(CO)3{P(OPh)2}2NR]. The molybdenum complexes are sensitive to air oxidation even in the solid state, whereas the tungsten complexes are more stable in the solid state and in solution. The structure of the tungsten complex [WI2(CO)3{P(OPh)2}2NPh] has been determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system with the space group Pna 2(1), a = 19.372 (2) angstrom, b = 11.511 (1) angstrom, c = 15.581 (1) angstrom, and Z = 4. Full-matrix least-squares refinement with 3548 reflections (I > 2.5-sigma-(I)) led to final R and R(w) values of 0.036 and 0.034, respectively. The complex adopts a slightly distorted pentagonal-bypyramidal geometry rarely observed for such a type of complexes; two phosphorus atoms of the diphosphazane ligand, two iodine atoms, and a carbonyl group occupy the equatorial plane, and the other two carbonyl groups, the apical positions

Palladium(II) complex of phosphinic amide, [Pd(Ph₂P(O)CH₂NPh)₂], and its catalytic investigation towards Suzuki-Miyaura cross-coupling reactions

1400-1403The reaction between aniline and chlorodiphenylphosphine in 2:1 molar ratio afforded the aminophosphine C6H5NHPPh2 (1) which on subsequent treatment with paraformaldehyde produced the methylene inserted product, Ph2P(O)CH2NHPh (2). Treatment of (2) with Pd(OAc)2 in 2:1 molar ratio produced the complex [Pd(Ph2P(O)CH2NPh)2] (3), which has been characterized by various spectroscopic and microanalysis data. The catalytic activity of complex (3) has been investigated in Suzuki-Miyaura cross-coupling reactions. The reactions of various aryl halides with phenylboronic acid using (<b style="mso-bidi-font-weight: normal">3) as a catalyst gave moderate (35–55%) to high yields (100%) of coupled products.<span style="font-family:AdvPSA88A; mso-bidi-font-family:AdvPSA88A;mso-bidi-language:EN-US" lang="EN-GB"> </span

Synthesis, structural characterization and Hirshfeld surface analysis of copper(I) complexes containing hemilabile-ferrocenylbisphosphine [Fe{C5H4P(C6H4CH2NMe2-o)2}2]

1081-1090The reactions of ferrocenylbisphosphine, [Fe{C5H4P(C6H4CH2NMe2-o)2}2] (1) comprising dangling amine functionalities with CuX yielded dinuclear complexes [{Cu2(μ-X)2}{Fe(C5H4P(C6H4CH2NMe2-o)2)2}] (2, X = Cl; 3, X = Br; 4 X = I). The reaction of 4 with pyridine affords a binuclear complex, [{Cu2I2(py)2}{Fe(C5H4P(C6H4CH2NMe2-o)2)2}] (5) (py = pyridine) in which each copper atom is tetracoordinated. Similarly, treatment of 4 with 2,2'-bipyridine in 1:1 molar ratio afforded the binuclear complex, [{Cu2I2(2,2′-bipy)}{Fe-(C5H4P(C6H4CH2NMe2-o)2)2}] (6). The equimolar reaction of 3 and 4,4'-bipyridine affords [{Cu2Br2(4,4′-bipy)}2{Fe(C5H4P- (C6H4CH2NMe2-o)2)2}2] (7) in good yield. The complexes 2 and 4 have been structurally characterized; both crystallize in the monoclinic space group with C2/c. In the crystal packing of 2 and 4, the invention-related intermolecular C-HX (X = Cl and I) and C-H(ring) interactions are primarily responsible for the crystal packing. A Hirshfeld surface analysis indicates that the most significant contributions to the crystal packing of 2 are from HH (81.7%), CH/HC (12.4%), ClH/HCl (4.3%) contacts, while those for 4 are from HH (80.9%), CH/HC (12.1%), IH/HI (5.4%) contacts