Coordination chemistry of a new tetratertiary phosphine ligand

Journal Article · Wed Jun 24 00:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00039a017· OSTI ID:7180851

Mason, M R; Duff, C M; Miller, L L; Jacobson, R A; Verkade, J G ^[1]

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1. Iowa State Univ., Ames (United States)

The synthesis and characterization of the new tetratertiary phosphine 2,3-bis[(diphenylphosphino)methyl]-1,4-bis(diphenylphosphino)butane (5) is reported. Oxidation of 5 with t-BuOOH or S[sub 8] yields the tetraphosphoryl and tetrathiophosphoryl derivatives 6 and 7, respectively. The molecular structure of 6 was confirmed by X-ray crystallography. Crystals of 6 are triclinic. The complexes [CH(CH[sub 2]PPh[sub 2])[sub 2]ML[sub n]][sub 2] have been prepared for ML[sub n] = PdCl[sub 2], PdBr[sub 2], PdI[sub 2], NiCl[sub 2], PtCl[sub 2], Cr(CO)[sub 4], Mo(CO)[sub 4], W(CO)[sub 4], and Fe(CO)[sub 3], in which 5 coordinates in a bis(bidentate) manner to two metals with the formation of two six-membered chelate rings. This coordination mode was confirmed by single-crystal X-ray diffraction studies on the complexes [CH(CH[sub 2]PPh[sub 2])[sub 2]ML[sub n]][sub 2] for ML[sub n] = PdCl[sub 2] and NiCl[sub 2]. Crystals of [CH(CH[sub 2]PPh[sub 2])[sub 2]PdCl[sub 2]][sub 2] are monoclinic. Crystals of [CH(CH[sub 2]PPh[sub 2])[sub 2]NiCl[sub 2]][sub 2] are triclinic. The monometallic complex (Ph[sub 2]P(O)CH[sub 2])[sub 2]CHCH(CH[sub 2]PPh[sub 2])[sub 2]PdCl[sub 2] was also synthesized. Crystals of this complex are orthorhombic. The monometallic complexes (5-P,P[prime],P[double prime])Mo(CO)[sub 3] were prepared in which 5 exhibits a tridentate (P,P[prime]P[double prime]) coordination mode and where the fourth P of 5 can have a lone pair or be bonded to O or S in addition to two phenyl groups. The monometallic complex (5)RhCl was also prepared, but [sup 31]P NMR spectroscopy indicated a complicated solution behavior for this complex. Similarly, attempted syntheses of monometallic complexes of Ni(II) and Pd(II) yielded mixtures which also exhibit complex behavior in solution as shown by [sup 31]P NMR spectroscopy.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 7180851
• Journal Information: Inorganic Chemistry; (United States), Vol. 31:13; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
LIGANDS
CHEMICAL PREPARATION
CHELATING AGENTS
CHROMIUM COMPLEXES
COORDINATION VALENCES
IRON COMPLEXES
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NICKEL COMPLEXES
NMR SPECTRA
ORTHORHOMBIC LATTICES
OXIDATION
PALLADIUM COMPLEXES
PHOSPHINES
PHOSPHORUS 31
PLATINUM COMPLEXES
TRICLINIC LATTICES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-EVEN NUCLEI
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE
400201* - Chemical & Physicochemical Properties