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Title: 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 · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00061a020· OSTI ID:6046945
; ;  [1]; ;  [2]
  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), Vol. 32:9; ISSN 0020-1669
Country of Publication:
United States
Language:
English