Dppm-Assisted synthesis and reactivity of bimetallic M-Mo, M-W, M-Co, and M-Mn (M = Pt, Pd) complexes. Crystal structure of [([eta][sup 2]-dppm)[ovr Pt([mu]-dppm)W](CO)[sub 2]Cp][PF[sub 6]][center dot]CH[sub 2]Cl[sub 2] (dppm = Ph[sub 2]PCH[sub 2]PPh[sub 2])

Journal Article · Wed Apr 28 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00061a020· OSTI ID:6046945

Braunstein, P; Oswald, B; Ries, M ^[1]; Lanfranchi, M; Tiripicchio, A ^[2]

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1. Universite Louis Pasteur, Strasbourg (France)
2. Universita di Parma (Italy)

Heterometallic carbonyl complexes and clusters were prepared by reaction of dppm (dppm = Ph[sub 2]PCH[sub 2]PPh[sub 2]) with linear trinuclear chain complexes trans-[Pt(or Pd)[l brace]m(CO)[r brace][sub 2](NCPh)[sub 2]] (m(CO) = Mo(CO)[sub 3]Cp, W(CO)[sub 3]Cp, Mn(CO)[sub 5], Co(CO)[sub 4]). The reaction of trans-[Pd[l brace]m(CO)[r brace][sub 2](NCPh)[sub 2]] with dppm afforded products having very different structures depending on the nature of the metal carbonyl fragment m(CO), as exemplified by the synthesis of the cationic bimetallic complexes [[ovr Pd([mu]-dppm)[sub 2]m]][sup +] (m = Mo(CO)[sub 2]Cp, 1[sup +]; m = W(CO)[sub 2]Cp, 2[sup +]), the neutral bimetallic [Cl[ovr Pd([mu]-dppm)[sub 2]M]n(CO)[sub 3]] (3a), and the trinuclear cluster [PdCo[sub 2](CO)[sub 5]([mu]-dppm)[sub 2]] (6). In contrast, the reaction of the Pt precursor trans-[Pt[l brace]m(CO)[r brace][sub 2](NCPh)[sub 2]] with dppm is much more selective, giving only bimetallic ionic complexes [([eta][sup 2]-dppm)[ovr Pt([mu]-dppm)m]][m(CO)] (m = Mo(CO)[sub 2]Cp, 7a; m = W(CO)[sub 2]Cp, 8a; m = Mn(CO)[sub 4], 9; m = Co(CO)[sub 3], 10). Exchange of the anions in 7a and 8a with PF[sub 6][sup [minus]] afforded [([eta][sup 2]-dppm)[ovr Pt([mu]-dppm)M]o(CO)[sub 2]Cp][PF[sub 6]] (7b) and [([eta][sup 2]-dppm)[ovr Pt([mu]-dppm)W](CO)[sub 2]Cp][PF[sub 6]] (8b), respectively, which are more soluble. The solid-state structure of the dichloromethane solvate of 8b has been determined by a single-crystal X-ray analysis. 29 refs., 3 figs., 5 tabs.

• OSTI ID: 6046945
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL PREPARATION
COBALT COMPLEXES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
LATTICE PARAMETERS
MAGNETIC RESONANCE
MANGANESE COMPLEXES
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PALLADIUM COMPLEXES
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
PLATINUM COMPLEXES
RESONANCE
SCATTERING
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRICLINIC LATTICES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION