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Reactions of Ru 3 (CO) 12 with Diphosphenes — A New Route to 50‐Electron Ru 3 P 2 nido ‐Clusters
Author(s) -
Freytag Matthias,
Edelmann Frank T.,
Ernst Ludger,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300363
Subject(s) - ruthenium , square pyramid , crystallography , chemistry , aryl , crystal structure , cluster (spacecraft) , stereochemistry , catalysis , biochemistry , alkyl , organic chemistry , computer science , programming language
The reaction of the symmetric diphosphene 2, 4, 6‐(CF 3 ) 3 ‐C 6 H 2 ‐P=P‐C 6 H 2 ‐2, 4, 6‐(CF 3 ) 3 4 with Ru 3 (CO) 12 led to the 50‐electron Ru 3 P 2 nido ‐cluster Ru 3 (CO) 9 [μ‐P‐C 6 H 2 ‐2, 4, 6‐(CF 3 ) 3 ] 2 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru 3 P 2 centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C 6 H 2 (CF 3 ) 3 groups is also appreciably distorted. Temperature‐dependent 19 F NMR studies of the [A 3 M 3 X] 2 spin system (A = M = CF 3 , X = 31 P) of 5 indicated a rotational barrier ΔG ≠ of 82.3 kJ mol ‐1 at 141 °C. The same Ru 3 P 2 core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru 3 (CO) 12 ; hindered rotation about the C(aryl)—P bonds was also observed, in this case.