Abstract
Diphosphorous (P2) side-on coordinated to a dicobalt (Co–Co) moiety was described 45 years ago. This discovery had several links to actual problems of homogeneous molecular catalysis. The new type of organometallic complexes induced several ingenious new ramifications in main-group/transition metal cluster chemistry in the last decades. The present review traces the main lines of these research results and their contacts to actual problems of industrial catalysis.
Highlights
Research Group for Petrochemistry of the Hungarian Academy of Sciences, H-8200 Veszprém, Department of Organic Chemistry, University of Pannonia, H-8200 Veszprém, Egyetem u. 10, Hungary; Department of Life Sciences, University of Modena and Reggio Emilia, I-4125 Modena, Via Campi, 103, Italy
These compounds, even if new at that time, were prepared as a part of important research trends, which were and are today intimately linked to very practical problems of homogeneous molecular catalysis
One of the related challenges was the recent discovery of the possibility of dinitrogen fixation by transition metal-based systems [6], and the related preparation of monometallic dinitrogen complexes [7] as well as the hypothesis that the biological nitrogen fixation proceeds through side-on coordination of the N2 molecule [8,9,10,11]
Summary
(μ2 -P2 )Co2 (CO) (Co–Co) (1) (Figure 1A) and (μ3 -S=P)Co3 (CO) (3Co–Co) (2) (Figure 2A) were reported [1,2] in 1973. The structure of 1 was confirmed by X-ray crystal diffraction of its triphenylphosphane derivative (μ2 -P2 )Co2 (CO) P(C6 H5 ) (Co–Co) (3) (Figure 1B) a few years later [3]; while the structure of 2 was based on infrared ν(C–O) spectroscopic analogy [4] (Figure 2B) These compounds, even if new at that time, were prepared as a part of important research trends, which were and are today intimately linked to very practical problems of homogeneous molecular catalysis. One of the related challenges was the (at that time) recent discovery of the possibility of dinitrogen fixation by transition metal-based systems [6], and the related preparation of monometallic dinitrogen complexes [7] as well as the hypothesis (which later became proved) that the biological nitrogen fixation proceeds through side-on coordination of the N2 molecule [8,9,10,11] Compounds 1 to 3 were early representatives of this research goal
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