Synthesis, structure and substitution reactions of a heterodimetallic tungsten - manganese complex [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4]

Martin J. Mays, Steven M. Owen, Paul R. Raithby, Paul F. Reinisch, Gregory P. Shields, Gregory A. Solan

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The room temperature reaction of [(η5-C5H5)W(CO)3(PPh2)] with [Mn(CO)5] in tetrahydrofuran (THF) followed by protonation with H3PO4 gives [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 as the major product. Among the identified minor products from this reaction are [Mn2(CO)9(PPh2H)] 2a, [Mn2(CO)9(PPh2PPh2)] 2b, [Mn2( μ-H)( μ-PPh2)(CO)8] 2c, and [Mn2( μ-PPh2)2(CO)8] 2d. 13CO reacts with complex 1 substituting both the manganese and tungsten carbonyl groups. In contrast, other two-electron donor ligands, L, only substitute the manganese carbonyl groups to give the substituted products [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)3L] (L = P(OMe)3 3a, PMe2Ph 3b, PMePh2 3c, PPh2H 3d), [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2L2] (L = P(OMe)3 4a or PMe2Ph 4b). In the case of the photolytic reaction of 1 with the diphosphine, dppm (dppm = Ph2PCH2PPh2), two products are obtained, one in which the ligand is chelated to the manganese centre, [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2(dppm)] 5, and the other in which the ligand bridges the tungsten manganese centres, [(η5-C5H5)(OC)W( μ-H)( μ-PPh2)( μ-dppm)Mn(CO)3] 6. Conversion of complex 5 to 6 can be achieved by prolonged UV irradiation of 5. A single crystal X-ray diffraction study for [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 is presented.

Original languageEnglish
Pages (from-to)123-134
Number of pages12
JournalJournal of Organometallic Chemistry
Issue number1-2
Publication statusPublished - 1 Feb 1997

Bibliographical note

Funding Information:
We thank the EPSRC (S.M.O., P.F.R., G.P.S. and G.A.S.) for financial support.


  • Crystal structure
  • Heterobimetallics
  • Hydrido
  • Manganese
  • Phosphido
  • Tungsten

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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