756866-15-6Relevant articles and documents
Five- and six-coordinate hydridorhodium(III) complexes containing metalated Schiff-bases as ligands
Meiswinkel, Andreas,Werner, Helmut
, p. 2855 - 2862 (2008/10/09)
The reactions of either [RhCl(C8H14) 2]2 (2) or [RhCl(C2H4) 2]2 (3) with Schiff-bases 1a-d derived from 2-aminopyridine afford, in the presence of four equivalents of PiPr3, the octahedral chloro(hydrido)rhodium(III) complexes [{(C5H 4N)N=C(C6H4R)}RhHCl(PiPr3) 2] (4a-d) in which the metalated Schiff-base behaves as a chelating ligand. Treatment of 4a (R=H) with NaI and CF3SO3Tl produce the corresponding derivatives [{(C5H4N)N=C(C 6H5)}RhHX(PiPr3)2] (5, 6) by salt metathesis. The triflato compound 6 reacts with nBu4NF·xH 2O to give [{(C5H4N)N=C(C6H 5)}RhHF(PiPr3)2] (7). While attempts to eliminate HCl from 4a failed, the reaction of 4a with AgPF6 generates the five-coordinate cationic complex [{(C5H4N)N=C(C 6H5)}RhH(PiPr3)2]PF6 (8) which adds one equivalent of acetonitrile to give [{(C5H 4N)N=C(C6H5)}RhH(NCCH3)(PiPr 3)2]PF6 (9). Treatment of 4a with either nBu2Mg or LiAlH4 affords the dihydridorhodium(III) compound [{(C5H4N)N=C(C6H5)}RhH 2(PiPr3)2] (10) being also accessible from 8 and nBu2Mg.