Unexpected Reaction of [ni(co)4-n(r2pcl)n] (n=1, 2, R=bu-tert, Cy, Ph) With Na2[fe2(co)8] - Synthesis and Electronic-structure of the Anions [fe2(mu-co)(co)6(mu-pr2)]- and Their Reactions With H+ and [m(pph3)]+ (m=cu, Ag, Au)

Walther, B.;Hartung, H.;Bottcher, HC.;Baumeister, U.;Schiebel, HM.;et.al.
(1991) Polyhedron — Vol. 10, n° 20-21, p. 2423-2435 (1991)

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Authors
  • Walther, B.
    Author
  • Hartung, H.
    Author
  • Bottcher, HC.
    Author
  • Baumeister, U.
    Author
  • Ladrière, JeanUCLouvain
    Author
  • Schiebel, HM.
    Author
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Abstract
Treatment of [Ni(CO)4-n(R2PCl)n] (n = 1, 2; R = Bu(t), Cy, Ph) with Na2[Fe2(CO)8] gave, depending on n and R, either the doubly phosphido-bridged complexes [Fe2(CO)6(mu-PR2)2] or the anions [Fe2(mu-CO)(CO)6(mu-PR2)]-. These anions can also be obtained by the reaction of [Fe(CO)4(PR2)]- with either [Fe2(CO)9] or [Fe(CO)5] via the intermediate [Fe2(CO)8(mu-PR2)]-. The electronic structure of the anions [Fe2(mu-CO) (CO)6(mu-PR2)]- has been studied by an EHT calculation which supports their ambident oxygen- or metal-nucleophilicity. The metal-centred nucleophilic reactions of the anion [Fe2(mu-CO)(CO)6(mu-PBu(t)2)]- with H+ and [M(PPh3)]+, (M = Cu, Ag, Au), respectively, are described. The new complexes have been characterized by various spectroscopic methods and the structure of [Fe2{mu-Ag(PPh3)}(mu-CO)(CO)6(mu-PBu(t)2)] has been established by X-ray analysis.
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Walther, B., Hartung, H., Bottcher, HC., Baumeister, U., Bohland, U., Reinhold, J., Sieler, J., Ladrière, J., & Schiebel, HM. (1991). Unexpected Reaction of [ni(co)4-n(r2pcl)n] (n=1, 2, R=bu-tert, Cy, Ph) With Na2[fe2(co)8] - Synthesis and Electronic-structure of the Anions [fe2(mu-co)(co)6(mu-pr2)]- and Their Reactions With H+ and [m(pph3)]+ (m=cu, Ag, Au). Polyhedron, 10(20-21), 2423-2435. https://doi.org/10.1016/S0277-5387(00)86204-X (Original work published 1991)