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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)
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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)
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.
Walther, B. ; Hartung, H. ; Bottcher, HC. ; Baumeister, U. ; Bohland, U. ; et. al. 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). In: Polyhedron, Vol. 10, no. 20-21, p. 2423-2435 (1991)