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Synthesis of chelating bidentate and tridentate cyano ligands and their complexes with Group VII metal carbonyls
Inorganic Chemistry
  • Daniel T. Plummer, Iowa State University
  • George A. Kraus, Iowa State University
  • Robert J. Angelici, Iowa State University
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Two new bidentate cyano ligands, DiCN-3 (2) and DEN-4 (3) (a,w-bis(2-cyanophenoxy)propane and -butane, respectively), have been prepared. These ligands and the ethane analogue DEN-2 (1) react with Mn(C0)5Br to afford complexes of the composition Mr~(cO)~(DicN-n)Br (n= 2, 9; n = 3, 10; n = 4, 11). Complexes 9 and 10 appear to be mononuclear and contain 13- and 14-membered chelate rings, respectively. Ligand 3 in 11 might be either chelated or bridged. IR studies of the reaction between 1-3 and Mn2(C0)6(CH&N)2(p-Br)2 show that, under identical conditions, more nitrile groups of 1 than of 2 and 3 are bound to the Mn(C0)3Br unit; this results suggests that DiCN-2 is a better chelating ligand than DiCN-3 or DiCN-4. A novel tricyano ligand, TriCN (1,3,5-tris(2-cyanophenyl)benzene (8)) has been synthesized from 2methylacetophenone. TriCN functions either as a bidentate ligand, as in M(CO)3(TriCN)Br (M = Mn, 12; M = Re, 14), or as a tridentate ligand, as in [M(CO),(TriCN)]PF6 (M = Mn, 13; M = Re, IS). Complexes 13 and 15 of TriCN are the first examples in which a tridentate cyano ligand chelates to a single metal center through its nitrogen lone pairs.

Reprinted (adapted) with permission from Inorganic Chemistry, 22(24); 3492-3497. Doi; 10.1021/ic00166a003. Copyright 1983 American Chemical Society.

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American Chemical Society
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Daniel T. Plummer, George A. Kraus and Robert J. Angelici. "Synthesis of chelating bidentate and tridentate cyano ligands and their complexes with Group VII metal carbonyls" Inorganic Chemistry Vol. 22 Iss. 24 (1983) p. 3492 - 3497
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