32826-10-1Relevant articles and documents
BASICITY OF METAL CARBONYL COMPLEXES XIX. CO SUBSTITUTION IN AZACYMANTRENE AND REACTIONS OF (η5-C4H4N)Mn(CO)2PPh3 WITH ELECTROPHILES. X-RAY CRYSTAL STRUCTURE OF 5-C4H4N)>2PdCl2
Pyshnograeva, N. I.,Batsanov, A. S.,Struchkov, Yu. T.,Ginzburg, A. G.,Setkina, V. N.
, p. 69 - 76 (1985)
A convenient method for substituting a CO ligand in azacymantrene, (η5-C4H4N)Mn(CO)3 (I), by the interaction of I with PPh3 in the presence of Me3NO has been found.The reactions of (η5-C4H4N)Mn(CO)2PPh3 (II) with electrophiles were studied.The nitrogen atom of the η-pyrrolyl ligand was shown to be the site having the largest basicity with respect to the proton (protonation in CF3COOH/CH2Cl2) and aprotic acids (Zn, Cd, Hg, Al, Ga, Sn, Pd salts) in II.The structure of the trinuclear complex 5-C4H4N)>2PdCl2 was established by an X-ray study: the crystals are monoclinic, a 9.0165(5), b 15.748(1), c 16.179(1) Angstroem, β 103.37(1) deg, Z = 2, space gropu P21/c; the palladium coordination environment is square-planar, Pd-N 2.033(2) and Pd-Cl 2.306(1) Angstroem.
SYNTHESES AND CARBON MONOXIDE SUBSTITUTION REACTIONS OF η5-N-HETEROCYCLE MANGANESE TRICARBONYLS
Ji, Liang-Nian,Kershner, David L.,Rerek, Mark E.,Basolo, Fred
, p. 83 - 94 (2007/10/02)
A new method of synthesis of η5-pyrrolyltricarbonylmanganese(I) is reported, along with the first syntheses of η5-indolyltricarbonylmanganese(I) and of η5-1-pyrindinyltricarbonylmanganese(I).Kinetic studies on CO substitution reactions of these η5-N-heterocyclic manganese carbonyls show that the reactions take place by a second-order process, first-order in metal complex and first-order in nucleophile.The most significant observation is that the N-heterocyclic compounds react faster than do their carbocyclic counterparts.This anticipated result is consistent with the greater electron-withdrawing ability of the N systems in the transition state for reaction, because N is more electronegative than is C.
