Synthesis, structure, and density functional theory analysis of a scandium dinitrogen complex, [(C(5)Me(4)H)(2)Sc](2)(mu-eta(2):eta(2)-N(2))

Selvan Demir; Sara E Lorenz; Ming Fang; Filipp Furche; Gerd Meyer; Joseph W Ziller; William J Evans

doi:10.1021/ja102681w

Synthesis, structure, and density functional theory analysis of a scandium dinitrogen complex, [(C(5)Me(4)H)(2)Sc](2)(mu-eta(2):eta(2)-N(2))

J Am Chem Soc. 2010 Aug 18;132(32):11151-8. doi: 10.1021/ja102681w.

Authors

Selvan Demir¹, Sara E Lorenz, Ming Fang, Filipp Furche, Gerd Meyer, Joseph W Ziller, William J Evans

Affiliation

¹ Department of Chemistry, University of California, Irvine, California 92697-2025, USA.

PMID: 20698681
DOI: 10.1021/ja102681w

Abstract

Investigation of the bis(tetramethylcyclopentadienyl) metallocene chemistry of scandium has revealed that the method involving reduction of trivalent salts with alkali metals used with lanthanides can also be applied to scandium to make a dinitrogen complex of the first member of the transition metal series. ScCl(3) reacts with 2 equiv of KC(5)Me(4)H to form (C(5)Me(4)H)(2)ScCl(THF), 1, which reacts with allylmagnesium chloride to make (C(5)Me(4)H)(2)Sc(eta(3)-C(3)H(5)), 2. Complex 2 reacts with [HNEt(3)][BPh(4)] to yield [(C(5)Me(4)H)(2)Sc][(mu-Ph)BPh(3)], 3, which has just one primary Sc-C(phenyl) contact connecting the tetraphenylborate anion and the metallocene cation. Treatment of 3 with KC(8) in THF under N(2) generates [(C(5)Me(4)H)(2)Sc](2)(mu-eta(2):eta(2)-N(2)), which has a coplanar arrangement of scandium and nitrogen atoms within a square planar array of tetramethylcyclopentadienyl rings. Density functional calculations explain the bonding that results in the 1.239(3) A N-N bond distance in the (N=N)(2-) moiety.